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Abstract:

A system for the production of conversion products from synthesis gas,
the system including a mixing apparatus configured for mixing steam with
at least one carbonaceous material to produce a reformer feedstock; a
reformer configured to produce, from the reformer feedstock, a reformer
product comprising synthesis gas comprising hydrogen and carbon monoxide
from the reformer feedstock; a synthesis gas conversion apparatus
configured to catalytically convert at least a portion of the synthesis
gas in the reformer product into synthesis gas conversion product and to
separate from the synthesis gas conversion product a tailgas comprising
at least one gas selected from the group consisting of carbon monoxide,
carbon dioxide, hydrogen and methane; and one or more recycle lines
fluidly connecting the synthesis gas conversion apparatus with the mixing
apparatus, the reformer, or both.

Claims:

1. A system for the production of conversion products from synthesis gas,
the system comprising: a mixing apparatus configured for mixing steam
with at least one carbonaceous material to produce a reformer feedstock;
a reformer configured to produce, from the reformer feedstock, a reformer
product comprising synthesis gas comprising hydrogen and carbon monoxide
from the reformer feedstock; a synthesis gas conversion apparatus
configured to catalytically convert at least a portion of the synthesis
gas in the reformer product into synthesis gas conversion product and to
separate from the synthesis gas conversion product a tailgas comprising
at least one gas selected from the group consisting of carbon monoxide,
carbon dioxide, hydrogen and methane; and one or more recycle lines
fluidly connecting the synthesis gas conversion apparatus with the mixing
apparatus, the reformer, or both.

2. The system of claim 1 comprising a recycle line fluidly connecting the
synthesis gas conversion apparatus with at least one burner of the
reformer, whereby at least a portion of the tailgas can be combusted to
provide heat.

3. The system of claim 1 wherein the at least one carbonaceous material
comprises biomass.

4. The system of claim 1 wherein the mixing apparatus is a pressure
vessel operable at a pressure of about 5 psig (34.5 kPa) to 45 psig
(310.3 kPa).

5. The system of claim 1 wherein the mixing apparatus comprises one or
more cylindrical vessels having a conical bottom section, an inlet for
superheated steam within the conical bottom section and an inlet for the
at least one carbonaceous material at or near the top of the cylindrical
vessel.

6. The system of claim 1 wherein the metallurgy of the reformer allows
operation at a reformer temperature greater than or equal to about
1700.degree. F. (926.degree. C.) and a reformer pressure greater than or
equal to about 5 psig (34.5 kPa).

7. The system of claim 1 wherein the reformer comprises: a cylindrical
vessel containing a plurality of vertically-oriented coiled tubes fluidly
connected with the mixing apparatus such that reformer feedstock may be
introduced thereto; at least one burner configured to combust fuel to
provide heat for the reforming and produce a flue gas; at least one
outlet for reformer product; and at least one outlet for the flue gas.

8. The system of claim 7 wherein each of the plurality of
vertically-oriented coiled tubes has a vertical height in the range of
from about 40 feet (12.2 m) to about 100 feet (30.5 m) and a coil length
at least 4 times the vertical height.

9. The system of claim 7 wherein the total coil length is in the range of
from about 4 to about 25 times the vertical height.

10. The system of claim 9 wherein the total coil length is in the range
of from about 4 to about 12 times the vertical height.

11. The system of claim 7 wherein least a portion of the plurality of
vertically-oriented coiled tubes have an inside diameter (ID) in the
range of from about 2 inches (5.1 cm) to about 4 inches (10.2 cm).

12. The system of claim 7 wherein the metallurgy of the coiled tubes
allows operation at a reformer pressure greater than or equal to about 45
psig (310.3 kPa).

13. The system of claim 7 wherein the at least one burner is positioned
substantially at, near, or below the bottom of the cylindrical vessel.

14. The system of claim 7 wherein the reformer comprises from about 1 to
about 10 burners.

15. The system of claim 7 wherein outlets of each of the
vertically-oriented coiled tubes are manifolded into an outlet for the
reformer product, wherein the manifold is positioned at, near, or below
the bottom of the cylindrical vessel.

16. The system of claim 7 wherein the at least one outlet for flue gas is
positioned at the top of the cylindrical vessel.

17. The system of claim 7 further comprising a steam superheater
configured to produce superheated steam utilizing heat transfer from the
reformer flue gas.

18. The system of claim 1 further comprising feed preparation apparatus
configured to comminute the at least one carbonaceous material, to dry
the at least one carbonaceous material, or both.

19. The system of claim 18 wherein the feed preparation apparatus
comprises at least one grinder and at least one separator configured to
provide a carbonaceous material having an average particle diameter of
less than about 3/16.sup.th of an inch (0.47 cm).

20. The system of claim 1 wherein the synthesis gas conversion apparatus
is configured to catalytically convert at least a portion of the
synthesis gas in the reformer product into synthesis gas conversion
product via contact of the at least a portion of the synthesis gas with
an iron-based Fischer-Tropsch catalyst.

Description:

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a divisional application which claims the
benefit under 35 U.S.C. §121 of U.S. patent application Ser. No.
12/976,763, filed Dec. 22, 2010, the disclosure of which is hereby
incorporated herein by reference in its entirety for all purposes.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

[0002] Not Applicable.

BACKGROUND

[0003] 1. Field of the Invention

[0004] This disclosure relates generally to a biorefinery and method for
the conversion of carbonaceous feedstock into synthesis gas conversion
products. More specifically, this disclosure relates to a biorefinery and
method for the conversion of carbonaceous feedstock to liquid
hydrocarbons via Fischer-Tropsch. Still more specifically, this
disclosure relates to a biorefinery and method for the conversion of
carbonaceous material to Fischer-Tropsch products wherein at least one
byproduct of Fischer-Tropsch conversion is utilized to produce additional
synthesis gas for Fischer-Tropsch synthesis.

[0005] 2. Background of the Invention

[0006] Processes for the production of synthesis gas from carbonaceous
materials utilize gasification of a feedstock comprising the carbonaceous
materials in a so-called `reformer` to produce a stream comprising
synthesis gas (i.e. hydrogen and carbon monoxide; also known as
`syngas`). The product synthesis gas generally also comprises amounts of
carbon dioxide and methane and may also comprise minor amounts of other
components. Generation of synthesis gas is disclosed in numerous patents.

[0007] Synthesis gas produced via gasification of carbonaceous materials
can be converted into other compounds in a so-called Fischer-Tropsch
reaction. Fischer-Tropsch (FT) synthesis can be used to catalytically
produce synthetic liquid fuels, alcohols or other oxidized compounds. FT
synthesis occurs by the metal catalysis of an exothermic reaction of
synthesis gas. Fischer-Tropsch (FT) technology can thus be utilized to
convert synthesis gas to valuable products. Hydrocarbon liquid products
of various Fischer-Tropsch processes are generally refined to produce a
range of synthetic fuels, lubricants and waxes. Often, the
Fischer-Tropsch process is performed in a slurry bubble column reactor
(SBCR). The technology of converting synthesis gas originating from
natural gas into valuable primarily liquid hydrocarbon products is
referred to as Gas To Liquids (GTL) technology. When coal is the raw
material for the syngas, the technology is commonly referred to as
Coal-To-Liquids (CTL). Fischer-Tropsch technology is one of several
conversion techniques included in the broader GTL/CTL technology.
Desirably, the synthesis gas for subsequent production of valuable
products via Fischer-Tropsch is produced from `green` materials. For
example, an environmentally-friendly system for the production of
synthesis gas, which may subsequently be utilized to produce
Fischer-Tropsch products, would desirably allow for the production of
synthesis gas from carbonaceous materials, such as biomass, which may
generally be considered waste materials

[0008] The catalyst used in the Fischer-Tropsch reactor and, to some
extent, the temperatures and pressures used will determine what products
can be obtained. Some Fischer-Tropsch processes are directed to the
production of liquid hydrocarbons. Such processes generally utilize
iron-, ruthenium, or cobalt-based catalysts. Iron-based catalysts are
generally operated with a synthesis gas having a molar ratio of hydrogen
to carbon monoxide in the range of from about 0.7 to about 2.0.
Cobalt-based catalysts are generally operated with a synthesis gas having
a mole ratio of hydrogen to carbon monoxide in the range of from about
1.8 to about 2.2. For example, carbon monoxide and hydrogen can be
converted to alkanes over a cobalt-thoria catalyst. U.S. Pat. No.
4,609,679 teaches the use of ruthenium combined with tantalum, niobium,
vanadium or mixtures thereof to selectively catalyze for the production
of methane. As mentioned hereinabove, other Fischer-Tropsch processes are
directed toward the production of alcohols.

[0009] Accordingly, there is a need in the art for systems and methods for
the production of synthesis gas conversion products from carbonaceous
materials. Such systems and methods should preferably enable the
environmentally-friendly production of synthesis gas conversion product,
for example by allowing the production of synthesis gas from sustainable
and renewable feedstocks such as biomass, facilitating sequestration of
carbon dioxide and/or reducing the amount of waste material produced.

SUMMARY

[0010] Herein disclosed are a system and method of producing synthesis gas
conversion product. Herein disclosed is a method of producing liquid
hydrocarbons, the method comprising: reforming a carbonaceous feedstock
that is solid, liquid, or both to produce a first synthesis gas
comprising hydrogen and carbon monoxide; subjecting at least a portion of
the first synthesis gas to Fischer-Tropsch conversion whereby at least a
portion of the hydrogen and carbon monoxide in the first synthesis gas is
catalytically converted into product comprising liquid hydrocarbons;
separating from the product a Fischer-Tropsch tailgas comprising at least
one component selected from carbon monoxide, hydrogen, methane and carbon
dioxide; and combusting at least a portion of the Fischer-Tropsch tailgas
to provide at least a portion of the heat for the reforming of additional
carbonaceous feedstock. The method may further comprise forming
additional carbonaceous feedstock by combining, with superheated steam,
at least one carbonaceous material and a spent catalyst stream comprising
Fischer-Tropsch liquid hydrocarbons and catalyst that has been at least
partially deactivated, attrited, or both during Fischer-Tropsch
conversion.

[0011] Also disclosed herein is a method of producing liquid hydrocarbons,
the method comprising: reforming a carbonaceous feedstock to produce a
first synthesis gas comprising hydrogen and carbon monoxide; subjecting
at least a portion of the first synthesis gas to Fischer-Tropsch
conversion whereby at least a portion of the hydrogen and carbon monoxide
in the first synthesis gas is catalytically converted into product
comprising liquid hydrocarbons; removing from the Fischer-Tropsch
conversion reactor a catalyst wax mixture comprising Fischer-Tropsch
liquid hydrocarbons and catalyst removed from the reactor; and combining
at least a portion of the catalyst wax mixture with at least one
carbonaceous material and superheated steam; and reforming the combined
material to produce additional synthesis gas. In embodiments, the method
further comprises combusting at least a portion of a Fischer-Tropsch
tailgas produced during Fischer-Tropsch conversion and comprising at
least one component selected from the group consisting of carbon
monoxide, hydrogen, carbon dioxide and methane to provide heat for
reforming of additional carbonaceous feedstock.

[0012] Also disclosed herein is a system for the production of conversion
products from synthesis gas, the system comprising: a mixing apparatus
configured for mixing steam with at least one carbonaceous material to
produce a reformer feedstock; a reformer configured to produce, from the
reformer feedstock, a reformer product comprising synthesis gas
comprising hydrogen and carbon monoxide from the reformer feedstock; a
synthesis gas conversion apparatus configured to catalytically convert at
least a portion of the synthesis gas in the reformer product into
synthesis gas conversion product and to separate from the synthesis gas
conversion product a tailgas comprising at least one gas selected from
the group consisting of carbon monoxide, carbon dioxide, hydrogen and
methane; and one or more recycle lines fluidly connecting the synthesis
gas conversion apparatus with the mixing apparatus, the reformer, or
both. In embodiments, the synthesis gas conversion apparatus is
configured to catalytically convert at least a portion of the synthesis
gas in the reformer product into synthesis gas conversion product via
contact of the at least a portion of the synthesis gas with an iron-based
Fischer-Tropsch catalyst.

[0013] In embodiments, the system comprises a recycle line fluidly
connecting the synthesis gas conversion apparatus with at least one
burner of the reformer, whereby at least a portion of the tailgas can be
combusted to provide heat. In embodiments, the at least one carbonaceous
material comprises biomass.

[0014] In embodiments, the mixing apparatus is a pressure vessel operable
at a pressure of about 5 psig (34.5 kPa) to 45 psig (310.3 kPa). In
embodiments, the mixing apparatus comprises one or more cylindrical
vessels having a conical bottom section, an inlet for superheated steam
within the conical bottom section and an inlet for the at least one
carbonaceous material at or near the top of the cylindrical vessel.

[0015] In embodiments the metallurgy of the reformer allows operation at a
reformer temperature greater than or equal to about 1700° F.
(926° C.) and a reformer pressure greater than or equal to about 5
psig (34.5 kPa). In embodiments of a system as disclosed herein, the
reformer comprises: a cylindrical vessel containing a plurality of
vertically-oriented coiled tubes fluidly connected with the mixing
apparatus such that reformer feedstock may be introduced thereto; at
least one burner configured to combust fuel to provide heat for the
reforming and produce a flue gas; at least one outlet for reformer
product; and at least one outlet for the flue gas.

[0016] In embodiments, each of the plurality of vertically-oriented coiled
tubes has a vertical height in the range of from about 40 feet (12.2 m)
to about 100 feet (30.5 m) and a coil length at least 4 times the
vertical height. In embodiments, the total coil length is in the range of
from about 4 to about 25 times the vertical height. In embodiments, the
total coil length is in the range of from about 4 to about 12 times the
vertical height. In embodiments, at least a portion of the plurality of
vertically-oriented coiled tubes have an inside diameter (ID) in the
range of from about 2 inches (5.1 cm) to about 4 inches (10.2 cm). In
embodiments, the metallurgy of the coiled tubes allows operation at a
reformer pressure greater than or equal to about 45 psig (310.3 kPa).

[0017] In embodiments, the at least one burner is positioned substantially
at, near, or below the bottom of the cylindrical vessel. In embodiments,
the reformer comprises from about 1 to about 10 burners. In embodiments,
outlets of each of the coiled tubes are manifolded into an outlet for the
reformer product, wherein the manifold is positioned at, near, or below
the bottom of the cylindrical vessel. In embodiments according to the
disclosure, the at least one outlet for flue gas is positioned at the top
of the cylindrical vessel. In embodiments, the system further comprises a
steam superheater configured to produce superheated steam via heat
transfer from the reformer flue gas.

[0018] In embodiments, the system further comprises feed preparation
apparatus configured to comminute the at least one carbonaceous material,
to dry the at least one carbonaceous material, or both. In embodiments,
the feed preparation apparatus comprises at least one grinder and at
least one separator configured to provide a carbonaceous material having
an average particle diameter of less than about 3/16th of an inch
(0.47 cm).

[0019] The foregoing has outlined rather broadly the features and
technical advantages of the invention in order that the detailed
description of the invention that follows may be better understood.
Additional features and advantages of the invention will be described
hereinafter that form the subject of the claims of the invention. It
should be appreciated by those skilled in the art that the conception and
the specific embodiments disclosed may be readily utilized as a basis for
modifying or designing other structures for carrying out the same
purposes of the invention. It should also be realized by those skilled in
the art that such equivalent constructions do not depart from the spirit
and scope of the invention as set forth in the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

[0020] For a more detailed description of embodiments of the present
invention, reference will now be made to the accompanying drawings,
wherein:

[0021] FIG. 1 is a schematic of a biorefinery suitable for carrying out
the production of synthesis gas conversion products according to an
embodiment of this disclosure;

[0022]FIG. 2 is a schematic of suitable mixing apparatus, biomass
reformer, and steam generation apparatus for use in the biorefinery of
FIG. 1 according to an embodiment of this disclosure;

[0023] FIG. 3 is a schematic of suitable mixing apparatus, biomass
reformer, and steam generation apparatus for use in the biorefinery of
FIG. 1 according to another embodiment of this disclosure;

[0024] FIG. 4 is a schematic of a synthesis gas cleanup and/or
conditioning apparatus suitable for use in the biorefinery of FIG. 1
according to an embodiment of this disclosure;

[0025]FIG. 5 is schematic of a feedstock handling and/or drying apparatus
suitable for use in the biorefinery of FIG. 1 according to an embodiment
of this disclosure;

[0026] FIG. 6 is a flow diagram of a method of producing synthesis gas
conversion product(s) according to an embodiment of this disclosure;

[0027] FIG. 7 is a flow diagram of a method of producing synthesis gas
according to an embodiment of this disclosure; and

[0028] FIG. 8 is a flow diagram of a method for converting synthesis gas
to product according to an embodiment of this disclosure.

NOTATION AND NOMENCLATURE

[0029] Certain terms are used throughout the following description and
claim to refer to particular system components. This document does not
intend to distinguish between components that differ in name but not
function.

[0030] As used herein, the term `carbonaceous feedstock` includes not only
organic matter that is part of the stable carbon cycle, but also
fossilized organic matter such as coal, petroleum, and natural gas, and
products, derivatives and byproducts thereof such as plastics, petroleum
coke and the like.

[0031] As used herein, the terms `hot`, `warm`, `cool` and `cold` are
utilized to refer to the relative condition of various streams. That is,
a `hot` stream is at a higher temperature than a `warm` stream, a `warm`
stream is likewise at a higher temperature than a `cool` stream and a
`cool` stream is likewise at a higher temperature than a `cold` stream.
Such a stream may not `normally be considered as such. That is a `cool`
stream may have a temperature that is actually high enough to be
considered hot or warm in conventional, non-relative usage.

[0032] As used herein the term `dry` as applied to a carbonaceous feed
material is used to indicate that the feed material has a moisture
content suitable for reforming, e.g. less than about 20 weight percent,
and not to imply the complete absence of moisture.

DETAILED DESCRIPTION

[0033] I. Overview. Herein disclosed are biorefinery and a method for
producing synthesis gas conversion products such as, but not limited to,
Fischer-Tropsch hydrocarbons. The disclosed biorefinery and method enable
the use of renewable and sustainable carbonaceous materials such as
biomass for the production of synthesis gas, the sequestration of carbon
dioxide in multiple ways and locations, a reduction in the amount of
waste for disposal (e.g. Fischer-Tropsch wax associated with spent
catalyst), and a reduction in the amount of `waste` tailgas. Accordingly,
the disclosed biorefinery and process for producing synthesis gas
conversion products therewith represent clean technologies. Such a
biorefinery is significantly more environmentally-friendly than
conventional biorefineries that produce synthesis gas for subsequent
conversion from other sources, such as from natural gas.

[0034] II. Biorefinery. FIG. 1 is a schematic of a biorefinery 100
according to this disclosure. Biorefinery 100 comprises mixing apparatus
300, reforming apparatus 400, steam generation apparatus 500 and
synthesis gas conversion apparatus 700. As discussed further hereinbelow,
biorefinery 100 can further comprise feed handling and/or drying
apparatus 200 and synthesis gas cleanup and/or conditioning apparatus
600. Each of the basic apparatus will be described in more detail
hereinbelow.

[0035] Reforming Apparatus 400. Biorefinery 100 comprises reforming
apparatus 400 (also at times referred to herein as `reformer 400`).
Description of reforming apparatus 400 will now be made with reference to
FIG. 2, which is a schematic of a portion 100A of a biorefinery
comprising mixing apparatus 300A, reformer 400A and steam generation
apparatus 500A, according to an embodiment of this disclosure and FIG. 3,
which is a schematic of a portion 100B of a biorefinery comprising mixing
apparatus 300B, reformer 400B and steam generation apparatus 500B,
according to another embodiment of this disclosure.

[0036] Reformer 400A is a high temperature, high efficiency reformer. In
embodiments, reformer 400 is a biomass reformer. Reformer 400A comprises
a plurality of coiled tubes 410A, 410B surrounded by enclosure,
cylindrical vessel or firebox 407. In embodiments, biomass reformer 400A
is a cylindrical vessel. In embodiments, the cylindrical vessel 407 has a
height H1 in the range of from about 40 feet (12.2 m) to about 100 feet
(30.5 m), from about 50 feet (15.2 m) to about 100 feet (30.5 m), or from
about 60 feet (18.3 m) to about 100 feet (30.5 m). In embodiments, coiled
tubes 410 have an inside diameter (ID) of at least or about 2 inches (5.1
cm), at least or about 3 inches (7.6 cm), or at least or about 4 inches
(10.2 cm). Coiled tubes 410 may be configured as cylindrical helices and
may be oriented vertically within cylindrical vessel 407. In embodiments,
each of the coiled tubes 410 has a total length or coil length that is at
least 4, 5, 10, 15, 20 or 25 times the vertical height of the coiled
tubes. In embodiments, each of the coiled tubes 410 has a total length in
the range of from about 200 feet (61 m) to about 900 feet (274 m), from
about 300 feet (91.4 m) to about 700 feet (213.4 m), or from about 350
feet (106.7 m) to about 650 feet (198.1 m).

[0037] In embodiments, the metallurgy of the coiled tubes is upgraded such
that the tubes are operable at the high temperatures of operation of a
high temperature reformer. A `high` temperature reformer is operable at a
temperature of at least 1093° C. (2000° F.). In
embodiments, the coiled tubes are operable at temperatures up to
926° C. (1700° F.), 982° C. (1800° F.),
1038° C. (1900° F.), 1093° C. (2000° F.),
1149° C. (2100° F.) and a pressure of at least 2 psig (13.8
kPa), 5 psig (34.5 kPa), at least 20 psig (137.9 kPa), greater than or
about 40 psig (275.8 kPa) or about 45 psig (310.3 kPa) or about 50 psig
(344.7 kPa). In embodiments, the coiled tubes are fabricated from
stainless steel or other high alloy steel, such as 310 stainless steel.
In embodiments, the coiled tubes are fabricated from austenitic
nickel-chromium-based superalloys or other high temperature alloys that
are resistant to hydrogen attack and suitable for production of coiled
helices, such as INCONEL®. In embodiments, the coiled tubes are
fabricated from INCONEL® 800 HT. In embodiments, the coiled tubes are
designed to provide at least 100,000 hours of operation.

[0038] As shown in FIG. 3, a distributor or flow divider 412 can be
positioned external or internal to firebox 407 for distributing a
reformer feedstock comprising a mixture of cooled steam and dry
carbonaceous material to the plurality of coiled tubes 410. In
embodiments, distributor 412 is positioned external to vessel 407. In
embodiments, distributor 412 is configured to provide substantially equal
amounts of the reformer feed mixture to each of the coiled tubes 410.

[0039] Distributor 412 distributes reformer feed mixture to each of the
plurality of coiled tubes 410 (410A and 410B indicated in the embodiment
of FIG. 3) via one or more reformer feed inlet lines 350 (350A and 350B
depicted in the embodiment of FIG. 3). In embodiments, mixing apparatus
300 (300A in FIG. 2; 300B in FIG. 3), further discussed hereinbelow,
comprises a plurality of feed mixers 310 (mixers 310A and 310B depicted
in FIG. 2; mixer 310C depicted in FIG. 3), the output of each of which is
fed via one or more reformer feed inlet lines 350 (350A and 350B
indicated in the embodiment of FIG. 2) into the coiled tubes 410.

[0040] The amount of superheated steam in the reformer feed mixture is a
function of the nature of the carbonaceous material (i.e. the feedstock)
used. In addition to steam necessary for carbonaceous feed transport,
steam provides the additional hydrogen necessary to produce, from the
feedstock, suitable synthesis gas for subsequent production of liquid
hydrocarbons, alcohols and/or other oxidized compounds, or other
synthesis gas conversion products therefrom. In terms of the
stoichiometric ratio of carbon to hydrogen in lower alcohols such as
methanol and ethanol and C5+ hydrocarbons, the dry feedstock may
have a stoichiometric excess of carbon relative to hydrogen. Thus water,
either trapped in the feedstock or in the form of superheated steam, or
both, can serve to provide additional hydrogen to maximize subsequent
production of synthesis gas conversion products. In embodiments, prior to
mixing, the feedstock is relatively dry, and sufficient water is provided
by combining superheated steam with the dried feedstock material in
mixing apparatus 300, as discussed hereinbelow.

[0041] In embodiments, from about 0.14 kilograms (0.3 pounds) to about
0.0.32 kilograms (0.7 pounds), from about 0.14 kg (0.3 pounds) to about
0.23 kg (0.5 pounds) or from about 0.14 kg (0.3 pounds) to about 0.18 kg
(0.4 pounds) of steam is added per pound of `dry` feedstock comprising
from about 4% to about 20% moisture by weight, from about 9% to about 18%
moisture or from about 10% to about 20% moisture, to provide the reformer
feed mixture that is introduced into the coiled tubes of the reformer.
The reformer feed mixture can have a total water to feedstock ratio in
the range of from about 0.1 to 0.5, from about 0.2 to about 0.45 or from
about 0.4 to about 0.5.

[0042] Feedstock reformation carried out in the feedstock reformer is
endothermic. Thus, reforming apparatus 400 comprises one or more burners
404 operable to provide the necessary heat of the pyrolysis, gasification
and/or reforming reaction(s) occurring within the coiled tubes 410 by
combusting fuel in the presence of oxygen.

[0043] Burners 404 are desirably positioned at or near the bottom of the
reformer. Burners 404 may be positioned internal or external to firebox
407. In embodiments, burner(s) 404 are internal to firebox 407. The
burner(s) 404 may be distributed substantially uniformly along the
diameter of vessel 407. In embodiments, the reformer has from about 1 to
about 10 burners, from about 1 to about 5 burners, or from about 1 to
about 2 burners. Oxidant utilized by the burner(s) may be provided as
air, enriched air, or substantially pure oxygen. For example, in the
embodiment of FIG. 2, each of the burners 404 is provided with air via
one or more air inlet lines 405 and fuel provided via one or more fuel
inlet lines 406. The oxidant and fuel may be fed separately to each
burner 404 or combined prior to entry thereto. The system can further
comprise a forced draft (FD) fan 409 configured to provide air to an air
preheater 413 configured to raise the temperature of the inlet air from a
first temperature (e.g. ambient temperature) to a temperature in the
range of from about -18° C. (0° F.) to about 399° C.
(750° F.), from about 38° C. (100° F.) to about
399° C. (750° F.) or from about 316° C. (600°
F.) to about 399° C. (750° F.). In embodiments, flue gas
exiting steam generation apparatus 500A (discussed further hereinbelow)
is utilized to heat the air upstream of burner(s) 404. The air may be
preheated by heat transfer with a flue gas stream in steam generator flue
gas outlet line(s) 570 exiting steam generator 501A. This flue gas may
have a temperature in the range of from about 649° C.
(1200° F.) to about 1260° C. (2300° F.), from about
760° C. (1400° F.) to about 1204° C. (2200°
F.) or from about 871° C. (1600° F.) to about 1149°
C. (2100° F.).

[0044] Fuel is provided to the one or more burners 404 via fuel inlet
line(s) 406. Any fuel known in the art can be utilized. In embodiments,
the fuel provided to the reformer is selected from the group consisting
of methane (e.g. natural gas), synthesis gas (e.g. excess synthesis gas),
tailgas (e.g. Fischer-Tropsch tailgas) and combinations thereof. As
discussed in detail hereinbelow, in embodiments comprising tailgas
recycle line(s) 770, one or more of the burners 404 may be specially
designed for burning tailgas or a mixture of tailgas with at least one
other gas such as methane or synthesis gas. The amount of air combined
with the fuel will be adjusted as known in the art based upon the fuel
utilized and the desired temperature within the reformer. In embodiments,
the reformer temperature is maintained at a temperature in the range of
at least 926° C. (1700° F.), 982° C. (1800°
F.), 1038° C. (1900° F.), 1093° C. (2000°
F.), 1149° C. (2100° F.).

[0045] For greater energy independence of the overall system, excess
synthesis gas can be made and used to run a turbine and generate
electricity to power the compressors and other electrically driven
devices.

[0046] The reformer comprises one or more reformer flue gas outlet lines
470 for flue gas exiting the reformer. Desirably, reformer flue gas
outlet line(s) 470 is positioned at or near the top of the reformer. In
the embodiment of FIG. 2, reformer flue gas outlet lines 470 are provided
a manifold 408 fluidly connecting reformer 400A with steam generation
apparatus 500A. The flue gas exiting reformer 400A can have a temperature
in the range of at least 926° C. (1700° F.), 982° C.
(1800° F.), 1038° C. (1900° F.), 1093° C.
(2000° F.), 1149° C. (2100° F.). The pressure of the
flue gas can be in the range of from about -20 inches H2O to 0 inch
H2O; from about -16 inches H2O to -2 inches H2O; or from
about -15 inches H2O to -5 inches H2O. In embodiments, the
reformer is configured for operation at a pressure of greater than or
equal to 5 psig (34.5 kPa), 30 psig (206.8 kPa), 40 psig (275.8 kPa), 45
psig (310.3 kPa) or 50 psig (344.7 kPa). Operation of the reformer at
higher pressures may allow a reduction in the number of compression
stages required upstream of the synthesis gas conversion apparatus 700
and/or a reduction in required compression horsepower.

[0047] Superheated steam from line(s) 550 carries the feedstock to the
reformer. In the process of heating up the feedstock upon mixing
therewith, the steam may cool to a temperature in the range of from about
150° F. (66° C.) to about 1000° F. (538° C.),
from about 200° F. (93° C.) to about 750° F.
(399° C.), or from about 300° F. (149° C.) to about
400° F. (204° C.). In the process of heating up the
feedstock upon mixing therewith, the steam may cool to a temperature of
approximately 204° C. (400° F.) as the reformer feed
mixture approaches the reformer. In embodiments, the inlet temperature of
the reformer feed mixture entering the reformer is at a temperature of
about 204° C. (400° F.). The exit temperature of the
synthesis gas leaving the reformer can be in the range of from about
870° C. (1600° F.) to about 1205° C. (2200°
F.) or from about 895° C. (1650° F.) to about 930°
C. (1700° F.). In embodiments, the reformer is operated at a
pressure in the range of from about 135 34.5 kPa (5 psig) to about 275.8
kPa (40 psig).

[0048] Within the coiled tubes of the reformer, the carbonaceous materials
in the reformer feed are anaerobically reformed with superheated steam to
produce a product process gas comprising synthesis gas (hydrogen and
carbon monoxide). The process gas can further comprise other components,
for example, methane, carbon dioxide, and etc. Minor amounts of other
ingredients may be formed. The reformer can comprise an internal (see
414A in FIG. 2) or external (see 414B in FIG. 3) manifold configured to
combine the process gas from each of the coiled tubes 410 into one or
more reformer process gas outlet lines 480. As indicated in the
embodiment of FIG. 2, outlet lines 402 associated with each of the coiled
tubes can be combined via manifold 414A to provide process gas to
reformer process gas outlet line 480. In embodiments, the reformer is
configured to provide temperature, pressure and residence time conditions
suitable to provide a process gas comprising synthesis gas having a
desired molar ratio of H2 to CO. In embodiments, the reformer is
configured to provide a synthesis gas having a H2:CO molar ratio in
the range of from about 0.7:1 to about 2:1, from about 0.7:1 to about
1.5:1 or about 1:1. In embodiments, the reformer is configured to provide
a residence time within the reformer in the range of from about 0.3 s to
about 3s, from about 0.3s to about 2s, from about 0.3s to about 1s, or
from about 0.4s to about 0.6s.

[0049] For any given feedstock, a desired composition of the resulting
process gas (i.e. the proportions of hydrogen, carbon dioxide, carbon
monoxide and methane) can be provided by adjusting the contact time in
the reformer, the temperature at the reformer outlet, the amount of steam
introduced with the feed, and to a lesser extent, the reformer pressure.
In embodiments, the synthesis gas is to be utilized downstream for the
production of liquid hydrocarbons via Fischer-Tropsch conversion. In
embodiments, the synthesis gas is to be utilized downstream for the
production of liquid hydrocarbons via Fischer-Tropsch conversion with an
iron-based catalyst. In such embodiments, the system may be operated with
a reformer exit temperature in the range of from about 898° C.
(1650° F.) to about 926° C. (1700° F.) and a
residence or contact time that is in the range of from about 0.3 seconds
to about 2.0 seconds in the reformer. The contact or residence time can
be calculated by dividing the internal volume of the reformer by the flow
rate of the process gas exiting the reformer.

[0051] As depicted in the embodiment of FIG. 2, mixing apparatus 300A can
comprise one or more mixers 310 (two mixers, 310A and 310B, indicated in
FIG. 2) configured to combine superheated steam with feedstock material.
Feedstock can be introduced into the mixing apparatus via one or more
feedstock inlet lines 250. The feedstock comprises at least one
carbonaceous material. In embodiments, the feedstock comprises biomass.
The feedstock can comprise, by way of non-limiting examples, lignite,
coal, red cedar, southern pine, hardwoods such as oak, cedar, maple and
ash, bagasse, rice hulls, rice straw, weeds such as kennaf, sewer sludge,
motor oil, oil shale, creosote, pyrolysis oil such as from tire pyrolysis
plants, used railroad ties, dried distiller grains, corn stalks and cobs,
animal excrement, straw, or some combination thereof. The hydrogen and
oxygen content for the various materials differ and, accordingly,
operation of the system (e.g. amount of superheated steam combined with
the feedstock in the mixing apparatus, the reformer temperature and
pressure, the reformer residence time) can be adjusted as known in the
art to provide a process gas comprising synthesis gas having a suitable
molar ratio of H2:CO for a desired subsequent synthesis conversion
application. The feedstock introduced into the mixing apparatus can have
an average particle size in the range of from about 3.9E-5 inch (0.0001
cm) to about 1 inch (2.54 cm), from about 0.01 inch (0.0254 cm) to about
0.5 inch (1.27 cm) or from about 0.09 inch (0.24 cm) to about 0.2 inch
(0.508 cm). In embodiments, the feedstock introduced into the mixing
apparatus has an average particle size of less than about 1 inch (2.54
cm), less than about 0.5 inch (1.27 cm) or less than about 3/16 inch
(0.48 cm). The feedstock introduced into the mixing apparatus can have a
moisture content in the range of from about 4 weight percent to about 20
weight percent, from about 5 weight percent to about 20 weight percent,
from about 10 weight percent to about 20 weight percent or from about 5
weight percent to about 18 weight percent. As discussed further
hereinbelow and mentioned hereinabove, a system of this disclosure can
further comprise, upstream of the mixing apparatus and connected
therewith via one or more lines 250, feedstock handling and/or drying
apparatus 200.

[0052] Within the mixing apparatus 300, feedstock is combined with
superheated steam to provide a reformer feed mixture. In the embodiment
of FIG. 2, feedstock in line 250 is divided via lines 250A and 250B and
introduced into mixers 310A and 310B respectively. Superheated steam,
which may be produced via steam generation apparatus 500 as further
described hereinbelow, is introduced via superheated steam lines 550,
550A and 550B to mixing apparatus 300A. In embodiments, one or more spent
catalyst recycle lines 755 is configured to directly or indirectly
recycle at least a portion of a catalyst/conversion product (e.g.
catalyst/wax or catalyst/alcohol) stream separated from the conversion
product within synthesis gas conversion apparatus 700 to the reformer, as
discussed further hereinbelow. In embodiments, the mixing apparatus is
configured to combine the feedstock in feedstock line 250 with
superheated steam having a temperature in the range of from about
400° F. (204.4° C.) to about 1000° F. (537.8°
C.), from about 600° F. (315.6° C.) to about 950° F.
(510° C.) or from about 400° F. (204.4° C.) to about
900° F. (482.2° C.) and/or a pressure in the range of from
about 150 psig (1034.2 kPa) to about 400 psig (2757.9 kPa), from about
200 psig (1378.9 kPa) to about 375 psig (2585.5 kPa) or from about 250
psig (1723.7 kPa) to about 350 psig (2413.2 kPa). In embodiments, a
system of this disclosure further comprises steam generation apparatus
500 configured to provide superheated steam for introduction into mixing
apparatus 300 as further described hereinbelow.

[0053] In the embodiment of FIG. 2, superheated steam is introduced into
each of the mixers 310A and 310B, respectively, via superheated steam
lines 550A and 550B. The reformer feed mixture comprising feedstock and
steam is introduced into the reformer via one or more reformer inlet
lines 350. The feedstock/steam mixture from each mixer 310 may be
introduced into a coiled tube 410. For example, in the embodiment of FIG.
2, feedstock/steam exiting mixers 310A and 310B via lines 350A and 350B,
respectively, are introduced into coiled tubes 410A and 410B,
respectively. In the embodiment of FIG. 3, the feedstock/steam mixture
exiting mixing vessel 310C of system 100B is introduced via line 350,
reformer feed distributor 412 and feed inlet lines 350A and 350B into
coiled tubes 410A and 410B, respectively. Other combinations of number of
mixers, manifolding of the outlets thereof, and distributors are
envisioned and not beyond the scope of this disclosure.

[0054] As indicated in FIG. 3, the mixing vessel 310C can be a cylindrical
vessel having a conical bottom 320. In embodiments, superheated steam is
introduced at or near the bottom or into a conical section 320 at or near
the bottom of the mixer. Feedstock may be introduced, in embodiments, at
or near the top of the mixer. In embodiments, the mixture exits out the
bottom of the mixing vessel.

[0055] In embodiments, the mixing vessel(s) (310A/310B/310C) are pressure
vessels configured for operation at a pressure in the range of from about
5 psig (34.5 kPa) to about 50 psig (344.7 kPa), from about 30 psig (206.8
kPa) to about 50 psig (344.7 kPa), from about 45 psig (310.3 kPa) to
about 50 psig (344.7 kPa), or configured for operation at or greater than
about 30 psig (206.8 kPa), 45 psig (310.3 kPa) or 50 psig (344.7 kPa). In
embodiments, the mixing vessels are configured for operation at a
temperature in the range of from about a temperature in the range of from
about 150° F. (66° C.) to about 1000° F.
(538° C.), from about 200° F. (93° C.) to about
750° F. (399° C.), or from about 300° F.
(149° C.) to about 400° F. (204° C.).

[0056] The mixing apparatus may be configured to provide a reformer feed
mixture by combining from about 0.3 pound of steam per pound of feedstock
to about 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1 pound of superheated steam per
pound of feedstock. In embodiments, the mixing apparatus is configured to
provide a reformer feed mixture by combining less than or equal to about
1 pound of superheated steam per pound of feedstock.

[0057] As indicated in FIG. 3 and discussed further hereinbelow, a portion
of the saturated steam exiting the steam generator via one or more steam
generator steam outlet line(s) 560 can be sent via one or more line(s)
560A and 560C to an excess steam condenser 516. Condensate from excess
steam condenser 516 can be combined with condensate from elsewhere in the
system (for example, with condensate in condensate outlet line 282 from a
dryer air preheater of feed handling and/or drying apparatus 200, as
discussed further hereinbelow). Condensate can be collected for disposal
and/or recycle and reuse via line 283.

[0059] Description of a suitable steam generation apparatus will now be
made with reference to FIG. 2. In the embodiment of FIG. 2, steam
generation apparatus 500A comprises reformer flue gas and reformer
effluent steam generator 501A and steam superheater 501B. Reformer flue
gas and reformer effluent steam generator 501A is configured to produce
saturated steam by heat transfer from the `hot` reformer effluent process
gas and the `warm` reformer flue gas exiting steam superheater 501B.
Reformer effluent process gas is introduced into reformer flue gas and
reformer effluent steam generator 501A via reformer process gas outlet
line(s) 480. The `hot` process gas introduced into reformer flue gas and
reformer effluent steam generator 501A via reformer process gas outlet
line(s) 480 may have a temperature in the range of from about 870°
C. (1600° F.) to about 1205° C. (2200° F.) or from
about 895° C. (1650° F.) to about 930° C.
(1700° F.). In embodiments, the `hot` process gas has a pressure
in the range of from about 34.5 kPa (5 psig) to about 275 KPa (40 psig).
Within reformer flue gas and reformer effluent steam generator 501A,
steam is commonly generated from the flue gas and the process gas,
although the two gases are not mixed. `Cool` reformer process gas leaves
reformer flue gas and reformer effluent steam generator 501A via steam
generator process gas outlet line(s) 450. The `cool` process gas exiting
reformer flue gas and reformer effluent steam generator 501A via steam
generator process gas line(s) 450 may have a temperature in the range of
from about 400° C. (752° F.) to about 800° C.
(1472° F.), from about 400° C. (752° F.) to about
600° C. (1112° F.) or about 400° C. (752° F.)
and/or a pressure in the range of from about 5 psig (34.5 kPa) to about
50 psig (344.7 kPa), from about 10 psig (68.9 kPa) to about 40 psig
(275.8 kPa) or from about 20 psig (137.9 kPa) to about 30 psig (206.8
kPa).

[0060] Reformer flue gas is introduced into reformer flue gas and reformer
effluent steam generator 501A via reformer flue gas outlet line(s) 470.
The `hot` flue gas introduced into reformer flue gas and reformer
effluent steam generator 501A via reformer flue gas outlet line(s) 470
may have a temperature in the range of from about 530° F.
(276.7° C.) to about 1500° F. (815.6° C.), from
about 530° F. (276.7° C.) to about 1200° F.
(648.9° C.) or about 530° F. (276.7° C.) and/or a
pressure in the range of from about -20 inches H2O to 0 inches
H2O; from about -15 inches H2O to about -5 inches H2O; or
from about -10 inches H2O to about -5 inches H2O. As depicted
in FIG. 2, in embodiments the reformer flue gas passes through steam
superheater 501B, as discussed further hereinbelow, prior to introduction
into reformer flue gas and reformer effluent steam generator 501A. In
such instances, the `warm` flue gas introduced into the reformer flue gas
and reformer effluent steam generator 501A may have a temperature in the
range of from about 1350° F. (732.2° C.) to about
2050° F. (1121.1° C.), from about 1450° F.
(787.8° C.) to about 1950° F. (1065.6° C.) or from
about 1350° F. (732.2° C.) to about 1850° F.
(1010° C.) and/or a pressure in the range of from about -20 inches
H2O to 0 inch H2O; -16 inches H2O to -5 inches H2O;
-15 inches H2O to 5 inches H2O. In embodiments, the temperature
of the `warm` flue gas is about 150 degrees less than that of the `hot`
flue gas, i.e. the flue gas temperature drop across 501B is in the range
of from about 130-170 degrees, from about 140-160 degrees, or about 150
degrees.

[0061] `Cool` reformer flue gas leaves reformer flue gas and reformer
effluent steam generator 501A via steam generator flue gas outlet line(s)
570. The `cool` flue gas exiting reformer flue gas and reformer effluent
steam generator 501A via steam generator flue gas outlet line(s) 570 may
have a temperature in the range of from about 50° F. (10°
C.) to about 400° F. (204.4° C.), from about 200° F.
(93.3° C.) to about 400° F. (204.4° C.) or about
400° F. (204.4° C.) and/or a pressure in the range of from
about -20 inches H2O to about 20 inches H2O; from about -16
inches to about 20 inches H2O; or from about -15 inches H2O to
about -10 inches H2O. Induced draft (ID) fan 573 can serve to draw
`cool` reformer flue gas exiting reformer flue gas and reformer effluent
steam generator 501A via steam generator flue gas outlet line(s) 570
through air preheater 413, discussed hereinabove. Heat transfer to the
air within air preheater 413 may provide a `cold` flue gas for use
elsewhere in the system, for example in a dryer air heater of a feed
handling and/or drying apparatus 200, as further discussed hereinbelow.
The `cold` flue gas passing out of air preheater 413 in line(s) 570 may
have a temperature in the range of from about -18° C. (0°
F.) to about 399° C. (750° F.), from about 38° C.
(100° F.) to about 399° C. (750° F.) or from about
316° C. (600° F.) to about 399° C. (750° F.)
and/or a pressure in the range of from about -20 inches H2O to about
20 inches H2O; from about -16 inches to about 20 inches H2O; or
from about -15 inches H2O to about -10 inches H2O.

[0062] One or more steam generator steam outlet lines 560 carries steam
(e.g. saturated steam) from reformer flue gas and reformer effluent steam
generator 501A. A portion of the saturated steam may be directed via one
or more steam export lines 560A for export to another apparatus or use
elsewhere in the system. As indicated in the embodiment of FIG. 2, all or
a portion of the saturated steam produced in reformer flue gas and
reformer effluent steam generator 501A can be directed to steam
superheater 501B configured to produce superheated steam. Steam
superheater 501B is configured to provide superheated steam at a
temperature in the range of from about 400° F. (204.4° C.)
to about 1000° F. (537.8° C.), from about 600° F.
(315.6° C.) to about 950° F. (510° C.) or from about
400° F. (204.4° C.) to about 900° F. (482.2°
C.) and/or a pressure in the range of from about 150 psig (1034.2 kPa) to
about 400 psig (2757.9 kPa), from about 200 psig (1379 kPa) to about 375
psig (2585.5 kPa) or from about 250 psig (1723.7 kPa) to about 350 psig
(2413.2 kPa). In embodiments, steam superheater 501B operates via heat
transfer from the `hot` reformer flue gas in reformer flue gas outlet
line(s) 470. Steam superheater 501B may be configured on a manifold or
header 408 comprising reformer flue gas outlet(s) 470. As mentioned
hereinabove, the `warm` flue gas exiting the steam superheater may have a
temperature in the range of from about 1500° F. (815.6° C.)
to about 2200° F. (1204.4° C.), from about 1600° F.
(871.1° C.) to about 2150° F. (1176.7° C.) or from
about 1600° F. (871.1° C.) to about 2100° F.
(1148.9° C.) and/or a pressure in the range of from about -20
inches H2O to 0 inches H2O; -16 inches H2O to -5 inches
H2O; -15 inches H2O to 5 inches H2O. As discussed
hereinabove, superheated steam exiting steam superheater 501B can be
introduced into the mixing apparatus 300 via one or more superheated
steam lines 550.

[0063] Reformer flue gas and reformer effluent steam generator 501A may,
as known in the art, be associated with one or more blowdown drums 515
configured to purge water off and control the solids level within
reformer flue gas and reformer effluent steam generator 501A.

[0064] Description of a suitable steam generation apparatus according to
another embodiment of this disclosure will now be made with reference to
FIG. 3. In the embodiment of FIG. 3, the steam generation apparatus 500B
comprises flue gas steam generator 501A'' and reformer effluent steam
generator 501A'. In the embodiment of FIG. 3, `hot` reformer effluent
process gas exiting reformer 400B via reformer process gas outlet lines
480 passes through reformer effluent steam generator 501A', configured
for transfer of heat from the `hot` reformer process gas to BFW
introduced thereto via BFW inlet line 580. `Cool` process gas exiting
reformer effluent steam generator 501A' via steam generator process gas
outlet line 450 may have a temperature in the range of from about
752° F. (400° C.) to about 1472° F. (800°
C.), from about 752° F. (400° C.) to about 1112° F.
(600° C.) or about 752° F. (400° C.) and/or a
pressure in the range of from about 5 psig (34.5 kPa) to about 50 psig
(344.7 kPa), from about 10 psig (68.9 kPa) to about 40 psig (275.8 kPa)
or from about 20 psig (137.9 kPa) to about 30 psig (206.8 kPa).

[0065] Reformer flue gas outlet line(s) 470 may fluidly connect reformer
400B with steam superheater 501B'. As discussed in regard to FIG. 2,
steam superheater 501B' is configured to produce superheated steam having
a temperature in the range of from about 400° F. (204.4°
C.) to about 1000° F. (537.8° C.), from about 600°
F. (315.6° C.) to about 950° F. (510° C.) or from
about 900° F. (482.2° C.) and/or a pressure in the range of
from about 150 psig (1034.2 kPa) to about 400 psig (2757.9 kPa), from
about 200 psig (1379 kPa) to about 375 psig (2585.5 kPa) or from about
250 psig (1723.7 kPa) to about 350 psig (2413.2 kPa). One or more
superheated steam lines 550 are configured to carry the superheated steam
from steam superheater 501B' to mixing vessel(s) 310C. The `warm` flue
gas exiting steam superheater 501B' has a temperature in the range of
from about 1350° F. (732.2° C.) to about 2050° F.
(1121.1° C.), from about 1450° F. (787.8° C.) to
about 1950° F. (1065.6° C.) or about 1850° F.
(1010° C.) and/or a pressure in the range of from about -20 inches
H2O to 0 inch H2O; -16 inches H2O to -5 inches H2O;
-15 inches H2O to 5 inches H2O and passes through flue gas
steam generator 501A'', configured for transferring heat from the `warm`
reformer flue gas to the steam in line 580A. One or more lines 560 are
configured to carry saturated steam exiting flue gas steam generator
501A''.

[0066] One or more steam generator flue gas outlet lines 570 are
configured to carry `cool` flue gas from flue gas steam generator 501A''.
As mentioned hereinabove, the `cool` flue gas exiting flue gas steam
generator 501A'' can have a temperature in the range of from about
50° F. (10° C.) to about 400° F. (204.4° C.),
from about 200° F. (93.3° C.) to about 400° F.
(204.4° C.) or about 400° F. (204.4° C.) and/or a
pressure in the range of from about -20 inches H2O to about 20
inches H2O; from about -16 inches to about 20 inches H2O; or
from about -15 inches H2O to about -10 inches H2O. As discussed
with regard to FIG. 2, the `cool` flue gas in steam generator flue gas
outlet line 570 may be used to heat combustion air in combustion air
preheater 413. Combustion air preheater 413 may be configured to heat air
introduced thereto via FD fan 406 and one or more air inlet lines 405
from a first lower temperature (e.g. ambient temperature) to a second
higher temperature in the range of from about from about 38° C.
(100° F.) to about 399° C. (750° F.), from about
316° C. (600° F.) to about 399° C. (750° F.)
or about 399° C. (750° F.) for introduction into the
reformer burner(s). `Cold` flue gas exiting air preheater 413 may have a
temperature in the range of from about -18° C. (0° F.) to
about 399° C. (750° F.), from about 38° C.
(100° F.) to about 399° C. (750° F.) or from about
316° C. (600° F.) to about 399° C. (750° F.)
and/or a pressure in the range of from about -20 inches H2O to about
20 inches H2O; from about -16 inches to about 20 inches H2O; or
from about -15 inches H2O to about -10 inches H2O. The `cold`
flue gas may be utilized elsewhere in the refinery, for example, in a
dryer air heater of a feed handling and/or drying apparatus, as further
discussed hereinbelow.

[0067] It will be apparent to those of skill in the art that flue gas
steam generator 501A'' and reformer effluent steam generator 501A' of the
embodiment of FIG. 3 may be combined within a single vessel as indicated
in the embodiment of FIG. 2.

[0069] Syngas cleanup and conditioning is a key technical barrier to the
commercialization of biomass gasification technologies and typically has
the greatest impact on the cost of clean synthesis gas. Generally, tar
reforming catalysts have not demonstrated that they can clean and
condition raw synthesis gas to meet the strict quality standards mandated
for economically feasible downstream production of products such as mixed
alcohols and liquid hydrocarbons therefrom. The synthesis gas cleanup and
conditioning apparatus disclosed herein can be utilized to overcome some
of these deficiencies.

[0070] Synthesis gas cleanup and/or conditioning apparatus 600 is
configured to remove undesirables, indicated to be removed via lines 660A
and 660B in FIG. 1, from the synthesis gas produced in the reformer (i.e.
to `cleanup` the synthesis gas) and provide a synthesis gas having a
desired composition for a particular downstream application (i.e. to
`condition` the synthesis gas). For example, synthesis gas cleanup and/or
conditioning apparatus 600 can be configured to remove one or more
undesirable components including, but not limited to, ash, carbon
dioxide, tar, methane, sulfur compounds, (excess) hydrogen and aromatics
from the reformer product, providing a cleaned up and conditioned
synthesis gas having a desired molar ratio of hydrogen to carbon monoxide
and acceptable levels of other components, including but not limited to,
carbon dioxide, ash, aromatics, methane, tars, carbon dioxide and etc.

[0071] In embodiments, synthesis gas cleanup and/or conditioning apparatus
600 comprises any combination of units known in the art to be suitable
for cleaning and conditioning synthesis gas for downstream
Fischer-Tropsch production of liquid fuels. In embodiments, synthesis gas
cleanup and/or conditioning apparatus 600 comprises one or more units
selected from ash removal apparatus, tar removal apparatus, aromatics
removal units, hydrogen adjustment units, carbon dioxide removal units,
and combinations thereof. In embodiments, synthesis gas cleanup and/or
conditioning apparatus 600 comprises a nickel dual fluid bed apparatus as
described in U.S. patent application Ser. No. 12/691,297, which is hereby
incorporated herein in its entirety for all purposes not contrary to this
disclosure.

[0072] FIG. 4 is a schematic of a synthesis gas cleanup and/or
conditioning apparatus 600A suitable for use in a biorefinery according
to embodiments of this disclosure. As indicated in the embodiment of FIG.
4, synthesis gas cleanup and/or conditioning apparatus can comprise one
or more of ash removal apparatus 605, tar removal apparatus 610,
aromatics removal apparatus 620, carbon dioxide removal apparatus 630 and
hydrogen adjustment apparatus 640. It is to be understood that a single
apparatus or type of apparatus may be configured to remove more than one
undesirable compound. For example, an aromatics removal unit may also
serve as a tar removal unit (e.g. a TEG unit) and/or a tar removal unit
may also serve as an ash removal unit (e.g. a venturi scrubber). It is
also noted that the order of the apparatus depicted in FIG. 4 may be
rearranged as known in the art depending on the specific units
incorporated into the system.

[0073] In embodiments, synthesis gas cleanup and/or conditioning apparatus
600 comprises ash removal apparatus 605. The ash removal apparatus 605 is
configured to remove ash from the synthesis gas produced in the reformer.
As some of the carbonaceous material used as feedstock for the production
of synthesis gas is not carbonaceous, the ash removal apparatus may serve
to remove such non-carbonaceous materials, such as phosphates and
minerals therefrom. Desirably, ash removal apparatus 605 reduces the
level of ash in the synthesis gas to less than 12 weight percent ash,
less than 6 weight percent ash or less than 2.3 weight percent ash. In
embodiments, ash removal apparatus 605 comprises one or more units
selected from cyclones, baghouses, and scrubbers (e.g. venturi scrubbers
or quench units). In embodiments, ash removal apparatus 605 comprises a
first cyclone configured to separate particles having an average particle
size of more than 1 μm, 100 μm, or 10000 μm from the synthesis
gas. In embodiments, ash removal apparatus 605 comprises a second cyclone
configured to remove particles having an average particle size of larger
1 μm, 100 μm, or 10000 μm from the synthesis gas exiting a first
cyclone.

[0074] As depicted in FIG. 4, the synthesis gas cleanup and/or
conditioning apparatus may comprise tar removal apparatus 610 and/or
aromatics removal apparatus 620. Any tar removal apparatus known in the
art may be utilized to reduce the level of tar in the synthesis gas.
Desirably, tar removal apparatus is configured to reduce the tar level in
the synthesis gas to less than 1.0 weight percent tar, less than 0.1
weight percent tar, less than 0.01 weight percent or less than 0.002
weight percent tar. In embodiments, the tar level in the synthesis gas is
reduced to less than 200 mg/L. In embodiments, the synthesis gas cleanup
and/or conditioning apparatus comprises a venturi scrubber, for example
downstream of one or more cyclone(s) or baghouses of an ash removal
apparatus 605. The venturi scrubber may be configured to wash out
water-soluble hydrocarbons, tars, aromatics such as benzene and any
remaining ash (e.g. fines that may have escaped upstream ash separation
via ash removal apparatus 605) from the synthesis gas. The venturi
scrubber may be configured for operation with a wash liquid. The wash
liquid may be water. Thus, a venturi scrubber may serve as ash removal
apparatus 605, a tar removal apparatus 610, and/or an aromatics removal
apparatus 620 (e.g. a benzene recovery unit) in a single unit. In
embodiments, the synthesis gas cleanup and/or conditioning apparatus
comprises one or more triethylene glycol units (TEG units) configured for
solvent extraction of tars and aromatics from the synthesis gas. In
embodiments, one or more TEG units are positioned downstream of one or
more cyclones of ash removal apparatus 605 and downstream of a venturi
scrubber ash removal unit 605/tar removal unit 610. The TEG unit may
serve as tar removal unit 610 and aromatics removal unit 620 in a single
apparatus. In embodiments, the TEG unit(s) removes remaining tars (e.g.
heavy tars) from the synthesis gas, reducing the tar level in the
synthesis gas to less than 1.0 weight percent, less than 0.1 weight
percent, or less than 0.01 weight percent. In embodiments, the TEG
unit(s) reduces the BTEX level in the synthesis gas to less than 0.5
weight percent, less than 0.05 weight percent, or less than 0.005 weight
percent. In embodiments, the BTEX level is reduced to less than or about
60, 50 or 45 mg/L.

[0075] As indicated in FIG. 4, synthesis gas cleanup and/or conditioning
apparatus 600A can comprise carbon dioxide removal apparatus 630. In
embodiments, the carbon dioxide removal apparatus reduces the carbon
dioxide content of the synthesis gas to less than 10 weight percent, less
than 1.0 weight percent or less than 0.1 weight percent. Any apparatus
known in the art for the removal of carbon dioxide from a synthesis gas
stream may be implemented in the biorefinery of this disclosure. In
embodiments, the synthesis gas cleanup and/or conditioning apparatus
comprises an acid gas removal unit (AGRU) configured to remove carbon
dioxide from synthesis gas introduced thereto. In embodiments, the
synthesis gas cleanup and/or conditioning apparatus comprises an amine
unit configured to remove hydrogen sulfide and carbon dioxide from
synthesis gas introduced thereto.

[0076] The amine unit(s) removes carbon dioxide from the syngas. In
embodiments, a pressure swing adsorbent (PSA) unit, discussed below in
connection with hydrogen removal, could be used instead of an amine
scrubber to remove the carbon dioxide. In an amine unit the synthesis gas
is scrubbed with an amine-based solvent in an absorption column. The
solvent is regenerated in a second column thereby releasing a high purity
CO2 product.

[0077] The carbon dioxide removal apparatus 630 serves as one point source
of carbon dioxide sequestration provided by the disclosed biorefinery.
The carbon dioxide removed from the synthesis gas may be sequestered and
sold, for example, for use in enhanced oil recovery (EOR), as known in
the art. Sulfur compounds that may be removed in the carbon dioxide
removal apparatus (e.g. via one or more AGRU's) may be used to produce
valuable commodities such as, but not limited to, fertilizer and sulfuric
acid. Sequestration of carbon dioxide in this manner is
environmentally-friendly, as it allows for a substantial reduction in the
amount of carbon dioxide, a `greenhouse` gas, that is ultimately disposed
via undesirable venting to the atmosphere.

[0078] As indicated in FIG. 4, the synthesis gas cleanup and/or
conditioning apparatus can comprise hydrogen adjustment apparatus 640.
Depending on the ultimate application intended for the synthesis gas,
adjustment of the hydrogen content in the synthesis gas may be desirable.
For example, for use in Fischer-Tropsch production of liquid hydrocarbons
via Fischer-Tropsch synthesis over an iron-based catalyst, it may be
desirable to remove hydrogen from the synthesis gas upstream of a
Fischer-Tropsch synthesis reactor in order to reduce the molar ratio of
hydrogen to carbon monoxide (e.g. to provide a hydrogen to carbon
monoxide molar ratio of about 1:1). Desirably, the reformer 400 is
operated with such a composition of feed (i.e. moisture and/or steam
content) and at appropriate temperature, pressure, and residence time
that the synthesis gas produced therein has the desired molar ratio of
hydrogen to carbon monoxide. However, in embodiments, subsequent hydrogen
adjustment may be necessary to provide a desired ratio for introduction
into subsequent Fischer-Tropsch processes.

[0079] In embodiments, hydrogen adjustment apparatus 640 is configured to
increase the molar ratio of hydrogen to carbon monoxide in the synthesis
gas (i.e. to increase the hydrogen content). In such embodiments,
hydrogen adjustment apparatus 640 may comprise a water gas shift reactor
(WGSR)configured to produce additional hydrogen and carbon dioxide from
water and some of the carbon monoxide in the synthesis gas, as known in
the art. In such embodiments, it may be desirable to position the WGSR
upstream of the carbon dioxide removal apparatus 630 in order to allow
subsequent removal of the carbon dioxide produced in the WGSR. In
embodiments, hydrogen adjustment apparatus 640 is configured to decrease
the molar ratio of hydrogen to carbon monoxide in the synthesis gas (i.e.
to decrease the hydrogen content). In such embodiments, the hydrogen
adjustment apparatus 640 may comprise a hydrogen membrane or pressure
swing absorber (PSA), as known in the art, configured to remove hydrogen
from the synthesis gas.

[0080] In embodiments, hydrogen adjustment apparatus comprises at least
one PSA, as mentioned hereinabove with regard to carbon dioxide removal.
In embodiments incorporating a PSA, the synthesis gas can be compressed
in one or more compressors, for example to a pressure of between 6895 KPa
(1000 psi) and 16,547 KPa (2400 psi), and the resulting compressed
synthesis gas stream fed to the PSA unit(s) configured to remove a
portion of the hydrogen from the synthesis gas.

[0081] Pressure swing adsorption (PSA) is an adiabatic process and is
applied for partial hydrogen removal from synthesis gas by removing some
of the hydrogen by adsorption through suitable adsorbents in fixed beds
contained in pressure vessels under high pressure. Regeneration of
adsorbents is accomplished by countercurrent depressurization and by
purging at low pressure with previously recovered hydrogen gas. To obtain
a continuous flow of product, a minimum of two adsorbers may be utilized,
such that at least one adsorber is receiving feed syngas. Simultaneously,
the subsequent steps of depressurization, purging and repressurization
back to the adsorption pressure are executed by the other adsorber(s).
After such adsorbent regeneration and repressurization the adsorber is
switched onto adsorption duty, whereupon another adsorber is regenerated.
For removing hydrogen, the adsorbent used is generally silica gel.

[0082] An alternative type of hydrogen separator which might be used to
separate a portion of the hydrogen from the synthesis gas in synthesis
gas cleanup and/or conditioning 600 is a hydrogen specific permeable
membrane separator.

[0083] Synthesis Gas Conversion Apparatus 700. The biorefinery of this
disclosure further comprises synthesis gas conversion apparatus 700. As
depicted in FIG. 1, synthesis gas conversion apparatus 700 is located
downstream of synthesis gas cleanup and/or conditioning apparatus 600. In
embodiments, synthesis gas conversion apparatus 700 is any suitable
synthesis gas conversion apparatus known in the art for the production of
valuable products (e.g. liquid hydrocarbons, ethanol, methanol, mixed
alcohols) from synthesis gas. By way of nonlimiting examples, the
synthesis gas conversion apparatus can comprise at least one selected
from Fischer-Tropsch reactors, alcohol synthesis reactors and microbial
alcohol synthesis reactors. In embodiments, synthesis gas conversion
apparatus 700 comprises a Fischer-Tropsch reactor configured for the
production of liquid hydrocarbons from synthesis gas. In embodiments, the
Fischer-Tropsch reactor configured for the production of liquid
hydrocarbons from synthesis gas is configured to operate with and/or
contains an iron-based FT catalyst or a cobalt-based FT catalyst. In
embodiments, the FT catalyst is an iron-based catalyst formed as
described in or having the composition of FT catalyst described in U.S.
Pat. No. 5,504,118 and/or U.S. patent applications Ser. No. 12/189,424;
12/198,459; 12/207,859; 12/474,552; and/or 12/790,101, the disclosures of
each of which are hereby incorporated herein in their entirety for all
purposes not contrary to this disclosure.

[0084] As indicated in FIG. 1, one or more conversion product outlet lines
750 are configured for the removal of conversion product from synthesis
gas conversion apparatus 700. In embodiments, the conversion product
comprises primarily liquid hydrocarbons. In embodiments, the conversion
product comprises primarily alcohols. In embodiments, the conversion
product comprises primarily Fischer-Tropsch hydrocarbons having five or
more carbon atoms (i.e. C5+ hydrocarbons). In embodiments, a spent
catalyst recycle line 755 is configured to directly or indirectly recycle
at least a portion of a catalyst/conversion product (e.g. catalyst/wax or
catalyst/alcohol) stream separated from the conversion product within
synthesis gas conversion apparatus 700 to the reformer. For example,
spent catalyst recycle line 755 may fluidly connect synthesis gas
conversion apparatus 700 with feedstock inlet line 250 such that the
catalyst/product may be combined with superheated steam in mixing
apparatus 300 and subsequently introduced into the reformer. At the high
temperatures of operation of the reformer, even long chain hydrocarbons
(i.e. wax) in a conversion product can be easily converted into
additional synthesis gas. In this manner, the hydrocarbons and/or other
conversion products in the catalyst/product can be converted to
additional synthesis gas, thus improving the overall liquid yields from
the system. Additionally, as spent catalyst is typically sent for
disposal, for example, in a landfill and since incorporation into the
biorefinery of this disclosure of such a spent catalyst recycle line
enables the spent catalyst to be separated in the ash (for example, via
ash removal in the synthesis gas cleanup and/or conditioning apparatus),
such recycle enables a reduction in the amount of waste material that
must ultimately be disposed. In embodiments, the overall liquid yield
from a biorefinery of this disclosure comprising a Fischer-Tropsch
reactor configured for the production of liquid hydrocarbons is in the
range of from about 0.5 to about 1.4 barrels, from about 0.6 to 2
barrels, or from about 0.6 to about 1.5 barrels of conversion product per
dry ton of feed material. In embodiments, the overall liquid yield from a
biorefinery of this disclosure is greater than or equal to about 0.4,
0.5, 0.6, 0.7 0.8, 0.9, 1.0, 1.1, 1.2, 1.3 or 1.4 barrels (16.8, 21,
25.2, 29.4, 33.6, 37.8, 42, 46.2, 50.4, 54.6, or 58.8 gallons) of
Fischer-Tropsch conversion product per dry ton of feed material.

[0085] As indicated in FIG. 1, one or more tailgas outlet lines 760 are
configured to remove tailgas from synthesis gas conversion apparatus 700.
The tailgas can comprise carbon monoxide, hydrogen, methane, carbon
dioxide and possibly other components. In the biorefinery of this
disclosure, at least a portion of the tailgas produced in synthesis gas
conversion apparatus 700 may beneficially be recycled via one or more
tailgas recycle lines 770 to reformer 400 for use as fuel in the
burner(s) thereof. In embodiments, the one or more tailgas recycle lines
770 fluidly connect the one or more tailgas outlet lines 760 with one or
more of the one or more fuel inlet lines 406 feeding the one or more
burners 404 configured to provide heat to the reformer. In embodiments,
the one or more tailgas recycle lines 770 fluidly connect the one or more
tailgas outlet lines 760 directly with one or more of the one or more
burners 404. In this manner, a `waste` stream that is generally
considered of little value (i.e. tailgas) can be utilized to benefit in
the disclosed biorefinery. It is envisioned that, in embodiments, the
biorefinery further comprises a dedicated carbon dioxide removal
apparatus such that carbon dioxide may be extracted from all or a portion
of the tailgas exiting synthesis gas conversion apparatus 700 via line
760 and/or all or a portion of the tailgas recycled via tailgas recycle
line(s) 770 and/or that a carbon dioxide removal apparatus of synthesis
gas cleanup and/or conditioning apparatus 600 is utilized to remove
carbon dioxide therefrom. In this manner, the biorefinery and method of
producing conversion product therefrom may be made even more `green`, by
enabling sequestration of additional carbon dioxide. Accordingly, in
embodiments, tailgas recycle line(s) 770 is fluidly connected with an
acid gas removal unit (AGRU) configured for the removal of carbon dioxide
therefrom prior to introduction of the recycle tailgas into one or more
burner(s) of the reformer. In embodiments, an AGRU is positioned
downstream of synthesis gas conversion apparatus 700 such that all or a
portion of the tailgas exiting synthesis gas conversion apparatus 700 via
tailgas outlet line(s) 760 can be introduced thereto and carbon dioxide
removed therefrom. In embodiments, an AGRU positioned downstream of
synthesis gas conversion apparatus 700 is configured to reduce the carbon
dioxide content of the tailgas to less than 10 weight percent, less than
1.0 percent or less than 0.1 percent. In embodiments, membrane technology
is utilized to remove carbon dioxide from at least a portion of the
tailgas exiting the synthesis gas conversion apparatus 700 via tailgas
outlet line(s) 760 and/or from at least a portion of the tailgas utilized
as fuel in one or more burner(s) associated with the reformer. Such
carbon dioxide removal from the tailgas can provide another point source
for carbon dioxide sequestration within the disclosed biorefinery. In
embodiments, at least a portion of the carbon dioxide-reduced tailgas
(containing combustible material) is recycled as fuel to the reformer.

[0086] Although not specifically discussed herein, one of skill in the art
would understand that various other units may be utilized in the
disclosed biorefinery. For example, in embodiments, synthesis gas
compression apparatus (e.g. synthesis gas booster compressor), as known
in the art, is positioned upstream of synthesis gas conversion apparatus
700.

[0087] Feed Handling and/or Drying Apparatus 200. A biorefinery of this
disclosure may further comprise feed handling and/or drying apparatus
configured to provide feed material of a desired average particle size,
composition and/or moisture content to the downstream mixing apparatus.
In embodiments, the feed handling and/or drying apparatus is
substantially as disclosed in U.S. Pat. No. 7,375,142, the disclosure of
which is hereby incorporated herein in its entirety for all purposes not
contrary to this disclosure.

[0088] Suitable feed handling and/or drying apparatus can comprise an
unloading and tramp metal removal zone I, a comminuting zone II, a drying
zone III, a reformer feed hopper zone, or some combination of two or more
thereof. A feed handling and/or drying apparatus will now be described
with reference to FIG. 5, which is a schematic of a feeding and drying
apparatus 200A according to an embodiment of this disclosure. Feed
handling and/or drying apparatus 200A comprises unloading and tramp metal
removal zone I configured for unloading of feed material and removal of
undesirables therefrom. Unloading and tramp removal zone I can comprise a
truck unloading hopper 205 into which delivered feed material is
deposited. Truck unloading hopper 205 may be associated with a tramp
metal detector 204 configured to determine the presence or absence of
undesirables such as metals in the feed material. Unloading and tramp
removal zone I can further comprise a conveyor 203 configured to convey
feed material onto a weigh belt feeder 206. A tramp metal separator 207
is configured to remove tramp metal and other undesirables from the feed
material introduced thereto. Removed undesirables can be introduced via
line 208 into and stored in a bin 209 for disposal.

[0089] Comminuting zone II can be positioned downstream of unloading and
tramp removal zone I, as indicated in FIG. 4, or can be downstream of an
unloading zone (i.e. in the absence of a tramp removal zone). Comminuting
zone II comprises apparatus configured to comminute the feed material. In
embodiments, the comminuting zone comprises at least one grinder 210. A
comminuting zone II may be used depending on the consistency of the
feedstock. In embodiments, the feedstock is primarily wood and/or other
organic material. Grinder 210 may be used if the feedstock is clumped
together, in unusually large conglomerates, or if the feedstock needs to
be further ground before being dried. After the feedstock is optionally
subjected to grinding, the ground material may be passed via grinder
outlet line 212 into one or more grinder discharge cyclones 220
configured to separate a larger average size fraction of feed material
from a smaller sized fraction. The larger sized fraction may be
introduced via one or more grinder discharge cyclone outlet lines 225
into one or more dryers 260 of dryer zone III configured to reduce the
moisture content of the material fed thereto. The smaller sized fraction
from grinder discharge cyclone 220 may be passed via grinder discharge
fines outlet line 222 and grinder discharge blower 230 into a dryer
baghouse 240 of drying zone III, as further discussed hereinbelow. In
embodiments, grinder discharge cyclone 220 is configured to provide
solids having a particle size of greater than 3/16'' (0.48 cm) into dryer
260 via grinder discharge cyclone outlet line 225. In embodiments,
grinder discharge cyclone 220 is configured to separate solids having a
particle size of less than 3/16'' (0.48 cm) into grinder discharge fines
outlet line 222. In embodiments, grinder discharge cyclone 220 is at
least about 93, 94, 95, 96 or at least about 97 percent.

[0090] Drying zone III comprises at least one dryer 260 configured to
reduce the moisture content of feed material introduced therein. In the
embodiment of FIG. 5, drying zone III comprises dryer 260, dryer air
heater 280, dryer cyclone 265, dryer baghouse 240, accumulator 245, dryer
exhaust fan 242 and dryer stack 246. Various embodiments may comprise any
combination of these components. Within drying zone III, the feedstock is
dried to a moisture content in the range of from about 5% to about 20%,
from about 5% to about 15% or from about 9% to about 15%. The flue gas
and air fed into dryer 260 mixes with comminuted feedstock to dry it,
purge it and heat it for further processing.

[0091] An air supply fan 261 is configured to introduce air via line 262
and reformer flue gas (e.g. `cold` reformer flue gas from air preheater
413) via line 570 into dryer air heater 280. The flue gas may be added
upstream of dryer air preheater 280 to prevent temperatures above
400° F. (204.4° C.) to the inlet of dryer 260, preventing
fire therein. As mentioned hereinabove, the `cold` flue gas may have a
temperature in the range of from about -18° C. (0° F.) to
about 399° C. (750° F.), from about 38° C.
(100° F.) to about 399° C. (750° F.) or from about
316° C. (600° F.) to about 399° C. (750° F.)
and/or a pressure in the range of from about -20 inches H2O to about
20 inches H2O; from about -16 inches to about 20 inches H2O; or
from about -15 inches H2O to about -10 inches H2O. In
embodiments, the flue gas introduced via line 570 comprises about 80%
nitrogen and 20% CO2.

[0092] A portion of the effluent steam from reformer effluent and reformer
flue gas steam generator 501A or from flue gas steam generator 501A'' can
be introduced via line 560A or 560D into dryer air preheater 280. The
steam introduced into dryer air preheater 280 may have a temperature in
the range of from about 150° F. (65.6° C.) to about
500° F. (260° C.), from about 250° F. (121.1°
C.) to about 450° F. (232.2° C.) or from about 300°
F. (148.9° C.) to about 400° F. (204.4° C.) and/or a
pressure in the range of from about 70 psig (482.6 kPa) to about 300psig
(2068.4 kPa), from about 150 psig (1034.2 kPa) to about 300 psig (2068.4
kPa) or from about 250 psig (1723.7 kPa) to about 300 psig (2068.4 kPa).
Condensate outlet line 282 is configured for removal of condensate from
air dryer 280. The pressure of the condensate may be reduced downstream
of the air dryer 280 and the condensate combined as indicated in FIG. 3
with condensate from excess steam condenser 516. Heated air exiting dryer
air heater 280 via heated air line 284 may have a temperature in the
range of from about -18° C. (0° F.) to about 204° C.
(400° F.), from about -18° C. (0° F.) to about
149° C. (300° F.) or from about -18° C. (0°
F.) to about 93.3° C. (200° F.). Desirably, the heated air
temperature does not exceed 400° F.

[0093] Heated air line 284 fluidly connects dryer air heater 280 with
dryer 260. Drying zone III may further comprise a heated air distributor
286 configured to divide heated air line 284 into a plurality of heated
air dryer inlet lines. For example, in the embodiment of FIG. 5,
distributor 286 divides the flow of air from heated air line 284 into
three heated air dryer inlet lines 284A-284C. Air passing through dryer
260 may comprise entrained feed material. Accordingly, drying zone III
can comprise one or more dryer cyclones 265 configured to separate solids
from the air exiting dryer 260. In the embodiment of FIG. 5, air exiting
dryer 260 via dryer vent lines 286A-286C is combined via air manifold 287
into dryer vent line 281 which is fed into dryer cyclone 265. It is to be
noted that, although three air inlet and air outlet (vent) lines are
shown in the embodiment of FIG. 5, any number of air inlet lines and
outlet lines may be utilized. Additionally, the number of air inlet lines
to dryer 260 need not be equal to the number of air outlet or vent lines.

[0095] One or more dryer baghouses 240 are configured to remove solids
from the air introduced thereto. One or more dryer baghouse solids outlet
lines 243 are configured to introduce solids separated within dryer
baghouse 240 into reformer feed hopper cyclone inlet line 276 of reformer
feed hopper zone IV, further discussed hereinbelow. In embodiments, dryer
baghouse 240 is configured to provide solids having a particle size of
greater than 20, 15, 10 or 5 μm into dryer baghouse solids outlet line
243. In embodiments, dryer baghouse 240 is configured to separate solids
having a particle size of less than 10 μm into dryer baghouse fines
outlet line 244.

[0096] One or more dryer baghouse fines outlet lines 244 are configured to
introduce gas from dryer baghouse 240 into dryer stack 246, optionally
via dryer exhaust fan 241 and line 247. A line 292 may introduce air into
an accumulator 245 prior to introduction into dryer baghouse(s) 240.

[0099] In embodiments, one or more purge lines 291 is configured to
introduce purge gas (e.g. flue gas or plant air) for purge into and push
feed material through reformer feed hopper 295. In embodiments, the purge
gas is flue gas comprising about 80% nitrogen and about 20% carbon
dioxide, helping to insure that the reformation process in reformer 400
will be carried out anaerobically. Reformer feed hopper 295 may also
include a vent for venting flue gas. From reformer feed hopper 295,
feedstock settles into feed hopper outlet line(s) 296, which extends from
the bottom of reformer feed hopper 295. The feedstock is metered by
rotary valve 297 into feedstock inlet line 250, along which it is
entrained with steam under pressure entering from superheated steam line
550 of mixing apparatus 300. To keep feedstock flowing into the stream of
steam, and in order to counter steam back pressure in line 250, a supply
of gas is moved through rotary feeder purge gas inlet line 288 via a
compressor to an inlet just below valve 297. To prevent the pressure in
feedstock inlet line 250 from blowing feedstock back into rotary valve
297, some of the gas is also split off from rotary feeder purge gas inlet
line 288 and fed to an inlet of mixing vessel rotary feeder 297. Rotary
feeder 297 includes a central rotor having a plurality of vanes which
divide the interior of valve 297 into separate compartments. Opposite the
inlet on rotary valve 297, is an outlet pressure vent line 289. As the
rotor of valve 297 rotates, the compartment formed by the vanes at the
top fill with feedstock. That filled compartment is then rotated until it
opens to the inlet, where it is pressurized with incoming gas. As the
rotor rotates further, the feedstock filled and pressurized chamber opens
into reformer feedstock inlet line 250. Since the pressure in the rotor
chamber is equalized with the pressure in line 250, the feedstock falls
down into feedstock inlet line 250. As the valve rotor continues on its
journey, it is eventually vented through outlet pressure vent line 289,
such that when the chamber again reaches feed hopper outlet line 296, it
is depressurized and will not vent back up into feed hopper outlet line
296. After feedstock has moved through rotary feeder valve 297 and into
feedstock line 250, it feeds by gravity into a mixing chamber or position
along mixing apparatus feedstock inlet line 250 where the feedstock is
mixed with superheated steam (e.g. steam having a temperature of about
510° C. (950° F.)) from superheated steam line 550.

[0101] The basic steps in the method of producing synthesis gas conversion
product according to this disclosure are depicted in the flow diagram of
FIG. 6. As indicated in FIG. 6, a method of producing synthesis gas
conversion product 801 comprises producing synthesis gas via reforming of
carbonaceous material at 800, cleaning up and/or conditioning the
synthesis gas at 900, converting the synthesis gas into product at 1000
and recycling at least one component from converting at 1000 for reuse in
the producing of synthesis gas at 800.

[0103] Preparing Carbonaceous Feedstock 810. In embodiments, preparing the
carbonaceous feedstock 810 comprises sizing (comminuting) at least one
carbonaceous feedstock such that it is of a desirable size for effective
reforming. In embodiments, preparing the carbonaceous feedstock comprises
reducing the average particle size of the feedstock to less than about
5/8th inch (15.9 mm), V2 inch (12.7 mm), or less than about
3/16th of an inch (4.8 mm). The carbonaceous feedstock may be sized
by any methods known in the art. In embodiments, a carbonaceous material
is sized by introducing it into one or more grinders 210, as discussed
above with reference to FIG. 5.

[0104] In embodiments, preparing the carbonaceous feed material comprises
drying the carbonaceous feedstock to a moisture content in the range of
from about 4 weight percent to about 20 weight percent, from about 5
weight percent to about 20 weight percent, from about 10 weight percent
to about 20 weight percent or from about 5 weight percent to about 18
weight percent. In embodiments, preparing the carbonaceous feedstock
comprises drying the carbonaceous feedstock to a moisture content of less
than about 25, 20, 15, 10 or 9 weight percent. The carbonaceous feedstock
may be dried by any methods known in the art. In embodiments, a
carbonaceous feedstock is dried by introducing it into one or more dryers
260, as discussed above with reference to FIG. 5. In embodiments, ground
carbonaceous material exiting grinder 210 is introduced into a grinder
discharge cyclone 220. Within grinder discharge cyclone 220, a stream of
larger sized particles is separated via grinder discharge cyclone outlet
line 225 from a stream of smaller sized particles in grinder discharge
fines outlet line 222. A grinder discharge blower 230 may introduce the
smaller particles separated in grinder discharge cyclone 220 into one or
more dryer baghouse(s) 240. The larger particles exiting grinder
discharge cyclone 220 via grinder discharge cyclone outlet line 225 are
introduced into dryer 260.

[0105] In embodiments, air supplied via air supply fan 261 and line 262 is
combined with flue gas in line 570 and introduced into dryer air heater
280. The flue gas utilized here may be produced during reforming of the
carbonaceous material discussed below. Heat transfer with steam
introduced into the dryer air heater via steam inlet line 560A/560D
produces heated air in heated air line 284 and condensate in condensate
outlet line 282. As discussed hereinabove, the steam utilized in dryer
air heater 280 may be produced via heat transfer with the hot reformer
process gas effluent and/or the `warm` flue gas effluent, as discussed
further hereinbelow.

[0106] Heated air in heated air line 284 may be divided by a heated air
distributor or divider 286 into a plurality of heated air inlet lines
284A-284C. Within dryer 260, the comminuted carbonaceous material is
dried to a desired moisture content, as mentioned hereinabove. Dryer
effluent comprising air and fines is introduced via dryer vent line 281
into dryer cyclone 265. Dried carbonaceous material exits dryer 260 via
one or more dried feed lines 294 and surge hopper 270. Air from reformer
feed hopper blower 275 may push comminuted and dried feed material from
dryer 260 and surge hopper 270 along reformer feed hopper inlet line 276
into reformer feed hopper cyclone 290. Solids removed from dryer cyclone
265 and dryer baghouse 240 may be introduced into reformer feed hopper
inlet line 276, as indicated in FIG. 5.

[0109] Preparing Reformer Feed 820. As discussed above, producing
synthesis gas via reforming of carbonaceous material 800 further
comprises preparing reformer feed 820. A suitable reformer feed may be
formed via combination of superheated steam and comminuted and dried
carbonaceous material via any methods known in the art. In embodiments,
spent catalyst comprising spent catalyst and associated synthesis gas
conversion product is combined with the carbonaceous material prior to or
along with combination with superheated steam. In embodiments, preparing
reformer feed comprises introducing the comminuted and dried carbonaceous
feed material and superheated steam into one or more mixing vessels as
described hereinabove.

[0112] As mentioned hereinabove, within the mixing apparatus, superheated
steam and carbonaceous material are combined to provide a reformer feed
mixture comprising from about 0.14 kilograms (0.3 pounds) to about 0.0.32
kilograms (0.7 pounds), from about 0.14 kg (0.3 pounds) to about 0.23 kg
(0.5 pounds) or from about 0.14 kg (0.3 pounds) to about 0.18 kg (0.4
pounds) of steam is added per pound of `dry` feedstock comprising from
about 4% to about 20% moisture by weight, from about 9% to about 18%
moisture or from about 10% to about 20% moisture, to provide the reformer
feed mixture that is introduced into the coiled tubes of the reformer. In
embodiments, the reformer feed comprises from about 0.01 wt % to about 20
wt %, from about 0.05 wt % to about 10 wt %, or from 1 wt % to about 5 wt
% weight percent spent catalyst/product (e.g. cat/wax). The reformer feed
may have a temperature in the range of from about 150° F.
(66° C.) to about 1000° F. (538° C.), from about
200° F. (93° C.) to about 750° F. (399° C.),
or from about 300° F. (149° C.) to about 400° F.
(204° C.). In embodiments, the reformer feed has a pressure of at
least or about in the range of from about 34.5 kPa (5 psig) to about 275
kPa (40 psig).

[0113] The superheated steam utilized in the reformer feed mixers may be
produced by heat exchange with the reformer flue gas effluent and/or the
reformer process gas effluent. With reference to FIG. 2, BFW may be
introduced via BFW inlet line(s) 580 into reformer effluent and reformer
flue gas steam generator 501A. Within reformer effluent and reformer flue
gas steam generator 501A, heat transfer between the hot gas (warm'
reformer flue gas passing through steam superheater 501B and `hot`
reformer process gas effluent) and the BFW may produce steam (in steam
outlet line 560) having a temperature in the range of from about
300° F. (148.9° C.) to about 500° F. (260°
C.), from about 350° F. (176.7° C.) to about 500° F.
(260° C.) or from about 350° F. (176.7° C.) to about
500° F. (260° C.) and a pressure in the range of from about
200 psig (1379 kPa) to about 300 psig (2068.4 kPa), from about 250 psig
(1723.7 kPa) to about 300 psig (2068.4 kPa), or from about 275 psig
(1896.1 kPa) to about 300 psig (2068.4 kPa). Steam exiting reformer
effluent and reformer flue gas steam generator 501A via steam generator
steam outlet line 560 may be divided, with a portion entering steam
superheater 501B via line 560B and another portion exported via line
560A. Within steam superheater 501B, heat transfer between `hot` reformer
flue gas and steam produces superheated steam having a temperature in the
range of from about 400° F. (204.4° C.) to about
1000° F. (537.8° C.), from about 600° F.
(315.6° C.) to about 950° F. (510° C.) or from about
400° F. (204.4° C.) to about 900° F. (482.2°
C.) and/or a pressure in the range of from about 150 psig (1034.2 kPa) to
about 400 psig (2757.9 kPa), from about 200 psig (1379 kPa) to about 375
psig (2585.5 kPa) or from about 250 psig (1723.7 kPa) to about 350 psig
(2413.2 kPa). The superheated steam exiting steam superheater 501B is
introduced into reformer feed mixing vessels 310A/310B via lines 550 and
550A/550B.

[0114] With reference to FIG. 3, BFW may be introduced via BFW inlet line
580 into reformer effluent steam generator 501A'. Within reformer
effluent steam generator 501A', heat transfer between the hot process gas
effluent and the BFW may produce steam. Steam exiting reformer effluent
steam generator 501A' via line 580A may be introduced into flue gas steam
generator 501A''. Within flue gas steam generator 501A'', heat transfer
between `warm` reformer flue gas and steam produces saturated steam
(exiting via steam generator steam outlet line 560) having a temperature
in the range of from about 300° F. (148.9° C.) to about
500° F. (260° C.), from about 350° F. (176.7°
C.) to about 500° F. (260° C.) or from about 350° F.
(176.7° C.) to about 500° F. (260° C.) and a
pressure in the range of from about 200 psig (1379 kPa) to about 300 psig
(2068.4 kPa), from about 250 psig (1723.7 kPa) to about 300 psig (2068.4
kPa), or from about 275 psig (1896.1 kPa) to about 300 psig (2068.4 kPa).

[0115] Reformer flue gas exiting the reformer via reformer flue gas outlet
line 470 passes through steam superheater 501W, wherein the temperature
of the `hot` flue gas is reduced to a temperature in the range of from
about 530° F. (276.7° C.) to about 1500° F.
(815.6° C.), from about 530° F. (276.7° C.) to about
1200° F. (648.9° C.) or about 530° F. (276.7°
C.) and/or a pressure in the range of from about -20 inches H2O to 0
inch H2O; from about -15 inch H2O to about -5 inch H2O; or
from about -10 inches H2O to about -5 inches H2O and
superheated steam are produced. The superheated steam may have a
temperature in the range of from about 400° F. (204.4° C.)
to about 1000° F. (537.8° C.), from about 600° F.
(315.6° C.) to about 950° F. (510° C.) or from about
400° F. (204.4° C.) to about 900° F. (482.2°
C.) and/or a pressure in the range of from about 150 psig (1034.2 kPa) to
about 400 psig (2757.9 kPa), from about 200 psig (1379 kPa) to about 375
psig (2585.5 kPa) or from about 250 psig (1723.7 kPa) to about 350 psig
(2413.2 kPa). The superheated steam exiting steam superheater 501W is
introduced into reformer feed mixing vessel 310C via line 550.

[0116] Reforming Reformer Feed 830. As discussed above, producing
synthesis gas via reforming of carbonaceous material 800 further
comprises reforming reformer feed at 830. In embodiments, reforming the
reformer feed 830 comprises converting the reformer feed into synthesis
gas via introduction into a reformer as described above. Reforming of the
synthesis gas will now be described with reference to FIGS. 2 and 3.
Reformer feed is introduced into the reformer via one or more reformer
feed inlet lines 350. In embodiments, a distributor 412 distributes the
reformer feed evenly among a plurality of coiled tubes 410. Within the
coiled tubes, reforming of the carbonaceous feedstock produces synthesis
gas. In embodiments, the temperature of the reformer (e.g. reformer
effluent) is maintained in the range of up to or about 926° C.
(1700° F.), 982° C. (1800° F.), 1038° C.
(1900° F.), 1093° C. (2000° F.), 1149° C.
(2100° F.). In embodiments, the pressure of the reformer is
maintained in the range of from about 0 psig (0 kPa) to about 100 psig
(689.5 kPa), from about 2 psig (13.8 kPa) to about 60 psig (413.7 kPa) or
from about 5 psig (34.5 kPa) to about 50 psig (344.7 kPa). In
embodiments, the reformer pressure is maintained at a pressure of equal
to or greater than about 2 psig (13.8 kPa), about 5 psig (34.5 kPa), or
about 50 psig (344.7 kPa).

[0117] The heat needed to maintain the desired reformer temperature is
provided to the endothermic reforming process by the combustion of fuel
in one or more burners 404. Air for the combustion may be heated in air
preheater 413 prior to burning with the fuel in burners 404. The fuel
combusted in the burner(s) 404 may be selected from tailgas (e.g.
Fischer-Tropsch tailgas), synthesis gas, methane (e.g. natural gas), and
combinations thereof. Desirably, at least a portion of the fuel combusted
in at least one of the burner(s) 404 comprises tailgas recycled from the
step of converting the synthesis gas into product 1000. At least one of
the burner(s) 404 may be specially designed for the combustion of tailgas
or for the combustion of tailgas in combination with another gas, for
example in combination with a as selected from synthesis gas and methane
(e.g. natural gas). In embodiments, recycle tailgas in line(s) 770 is
introduced into one or more burner(s) 404 by introduction into one or
more of the fuel lines 406 or via another fuel inlet line(s).

[0118] Cleaning Up and/or Conditioning Synthesis Gas 900. The method of
producing synthesis gas conversion products according to this disclosure
further comprises cleaning up and/or conditioning the synthesis gas at
900. Cleaning up and/or conditioning the synthesis gas comprises removing
one or more components from the synthesis gas. Cleaning up and/or
conditioning the synthesis gas can comprise removing one or more
components selected from the group consisting of ash, tar, aromatics,
carbon dioxide, hydrogen sulfide, carbon monoxide and hydrogen from the
synthesis gas. In embodiments, the synthesis gas is introduced into one
or more cyclones and/or baghouses for the removal of ash. The ash may be
reduced to a level of less than 10 weight percent, less than about 1.0
weight percent or less than about 0.1 weight percent. In embodiments, tar
is removed from the synthesis gas. In embodiments, the synthesis gas is
introduced into a venturi scrubber that serves to remove water-soluble
hydrocarbons, tar, ash fines that escaped the ash removal apparatus
and/or benzene from the synthesis gas.

[0120] In embodiments, conditioning comprises removing carbon dioxide from
the synthesis gas. In embodiments, an acid gas removal unit is utilized
to remove carbon dioxide and hydrogen sulfide from the synthesis gas. The
AGRU may be downstream of a TEG unit.

[0121] In embodiments, conditioning comprises subjecting the synthesis gas
to water gas shift by reaction of carbon monoxide in the synthesis gas
with water to produce carbon dioxide and additional hydrogen, thus
reducing the carbon monoxide content of the synthesis gas. In
embodiments, water gas shift provides a synthesis gas having a mole ratio
of hydrogen to carbon monoxide in the range of from about 0.5:1 to about
1.1:1, from about 0.7:1 to about 1.1:1, or about 1:1.

[0122] In embodiments for which the synthesis gas will be used at step
1000 for the production of liquid Fischer-Tropsch hydrocarbons, the
cleaned-up and conditioned synthesis gas may have a molar ratio in the
range of from about 0.5:1 to about 1.1:1, from about 0.7:1 to about
1.1:1, or about 1:1, a tar content of less than about 200 ppm (e.g.
˜95% removal), a carbon dioxide content of less than about 10
weight % (e.g. ˜95 percent removal), a sulfur content of less than
about 1 ppm, a BTEX content of less than about 50 ppm (e.g. ˜95%
removal), an ash content of less than about 0.1 weight percent, or a
combination thereof.

[0123] Converting Synthesis Gas into Product 1000. The method of producing
synthesis gas conversion product according to this disclosure further
comprises converting the synthesis gas into product at 1000. Desirably,
the conversion produces, in addition to valuable primary products, a
tailgas suitable for recycle to the step of producing synthesis gas via
reforming 800, as further discussed hereinbelow. In embodiments, the
tailgas comprises one or more gas selected from carbon dioxide, methane,
hydrogen (e.g. unreacted hydrogen) and carbon monoxide (e.g. unreacted
carbon monoxide).

[0124] The cleaned and/or conditioned synthesis gas is converted into
valuable products at 1000. This conversion may be referred to herein as
Fischer-Tropsch conversion. FIG. 8 is a flow diagram of a method 1000A
for converting synthesis gas to product, according to an embodiment of
this disclosure. Method 1000A comprises subjecting the synthesis gas to
reaction conditions whereby conversion products are formed 1010 and
separating tailgas and/or spent catalyst/product from the conversion
product(s) 1020.

[0125] Converting synthesis gas into product comprises subjecting the
synthesis gas to reaction conditions whereby conversion products are
formed. In embodiments, the synthesis gas is converted into products
consisting primarily of alcohols and/or other oxidized compounds.
Suitable reaction conditions including temperatures, pressures and
catalysts for such conversion are known in the art.

[0126] In embodiments, the synthesis gas is converted into products
consisting primarily of liquid hydrocarbons. In embodiments, the
synthesis gas is converted into products consisting primarily of C5+
hydrocarbons. In such embodiments, the synthesis gas may be compressed,
as needed, and introduced into one or more Fischer-Tropsch reactors
configured for the production of liquid hydrocarbons. In such
embodiments, subjecting the synthesis gas to reaction conditions whereby
conversion products are formed can comprise contacting the synthesis gas
with an FT catalyst that promotes the FT synthesis reactions at suitable
temperatures and pressures as known in the art.

[0127] In embodiments, the catalyst comprises at least one catalytically
active metal or oxide thereof. In embodiments, the catalyst further
comprises a catalyst support. In embodiments, the catalyst further
comprises at least one promoter. The catalytically active metal may be
selected from the group consisting of Co, Fe, Ni, Ru, Re, Os, and
combinations of two or more thereof. The support material may comprise
alumina, zirconia, silica, aluminum fluoride, fluorided alumina,
bentonite, ceria, zinc oxide, silica-alumina, silicon carbide, a
molecular sieve, or a combination of two or more thereof. The support
material may comprise a refractory oxide. The promoter may be selected
from Group IA, IIA, IIIB or IVB metals and oxides thereof, lanthanide
metals and metal oxides, and actinide metals and metal oxides. In
embodiments, the promoter is selected from the group consisting of Li, B,
Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, La, Ac, Ti, Zr, La, Ac, Ce and Th,
oxides thereof, and mixtures of two or more thereof. Suitable catalysts
may be as disclosed in U.S. Pat. Nos. 4,585,798; 5,036,032; 5,733,839;
6,075,062; 6,136,868; 6,262,131; 6,353,035; 6,368,997; 6,476,085;
6,451,864; 6,490,880; 6,648,662; 6,537,945; 6,558,634; and U.S. Patent
App. Pub. No. 2003/0105171; these patents and patent publications being
incorporated herein by reference for their disclosures of Fischer-Tropsch
catalysts and methods for preparing such catalysts.

[0128] The FT catalyst can be any suitable catalyst known in the art. In
embodiments, the FT catalyst is an iron-based catalyst formed as
described in or having the composition of an FT catalyst described in
U.S. Pat. No. 5,508,118 and/or U.S. patent applications Ser. No.
12/189,424; 12/198,459; 12/207,859; 12/474,552; and/or 12/790,101, the
disclosures of each of which are hereby incorporated herein in their
entirety for all purposes not contrary to this disclosure.

[0129] In embodiments, the FT catalyst is an iron-based catalyst
comprising iron, copper and potassium. The catalyst may have a weight
ratio of 100Fe:1Cu:1K (wt %:wt %:wt %), wherein the iron in the catalyst
comprises a maghemite:hematite weight ratio in the range of about 1%:99%
to about 70%:30%. The iron catalyst can comprise a maghemite to hematite
ratio of about 10%:90%. The catalyst can have a particle size
distribution in the range of 10 μm-100 μm. The catalyst can exhibit
a BET surface area in the range of from about 45 m2/g to about 150
m2/g or from about 45 m2/g to about 65 m2/g. The catalyst
can have a mean pore diameter in the range of from about 45 Å to
about 120 Å or from about 75 Å to about 120 Å. The catalyst
can have a mean pore volume in the range of from about 0.2 cc/g to about
0.6 cc/g or from about 0.20 cc/g to about 0.24 cc/g. The catalyst can
have a mean crystallite size in the range of from about 15 nm to about 40
nmor from about 25 nm to about 29 nm.

[0130] Depending on the preselected alpha, i.e., the polymerization
probability desired, a precipitated iron catalyst may have a weight ratio
of potassium (e.g., as carbonate) to iron in the range of from about
0.005 and about 0.015, in the range of from 0.0075 to 0.0125, or about
0.010. Larger amounts of alkali metal promoter (e.g., potassium) may
cause the product distribution to shift toward the longer-chain
molecules, while small amounts of alkali metal may result in a
predominantly gaseous hydrocarbon product.

[0131] The weight ratio of copper to iron in the iron Fischer-Tropsch
catalyst may be in the range of from about 0.005 and 0.050, in the range
of from about 0.0075 and 0.0125, or about 0.010. Copper may serve as an
induction promoter. In preferred embodiments, the weight ratio of Cu:Fe
is about 1:100.

[0132] The catalyst may be an iron Fischer-Tropsch catalyst comprising
structural promoter. The structural promoter may significantly reduce the
breakdown of the catalyst in a SBCR (slurry bubble column reactor). The
structural promoter may comprise silica, and may enhance the structural
integrity during activation and operation of the catalyst. In
embodiments, the catalyst comprises a mass ratio of SiO2:Fe of less
than about 1:100 when the structural promoter comprises silica and less
than about 8:100 when the structural promoter comprises silica sol.

[0133] In embodiments, the at least one structural promoter is selected
from oxides of metals and metalloids and combinations thereof. The
structural promoter may be referred to as a binder, a support material,
or a structural support.

[0134] Depending on the level of structural promoter comprising silicate
and the preselected alpha, i.e. the polymerization probability desired,
the weight ratio of K:Fe may be from about 0.5:100 to about 6.5:100, from
about 0.5:100 to about 2:100, or about 1:100.

[0135] In embodiments wherein the structural promoter comprises silica
sol, the weight ratio of iron to potassium is in the range of from about
100:1 to about 100:5. In embodiments, the weight ratio of iron to
potassium is in the range of from about 100:2 to about 100:6. In
embodiments, the weight ratio of iron to potassium is in the range of
from about 100:3 to about 100:5. In embodiments, the weight ratio of iron
to potassium is in the range of from about 100:4 to about 100:5. In some
preferred embodiments, the weight ratio of iron to potassium is in the
range of from about 100:2 to about 100:4. In embodiments, the weight
ratio of iron to potassium about 100:3. In embodiments, the weight ratio
of iron to potassium is about 100:5.

[0136] In embodiments wherein the structural promoter comprises silica
sol, the weight ratio of iron to copper may be in the range of from about
100:1 to about 100:7. In some embodiments, the weight ratio of iron to
copper is in the range of from about 100:1 to about 100:5. More
preferably, the weight ratio of iron to copper is in the range of from
about 100:2 to about 100:6. Still more preferably, the weight ratio of
iron to copper is in the range of from about 100:3 to about 100:5. In
some preferred embodiments, the weight ratio of iron to copper is in the
range of from about 100:2 to about 100:4. In other specific embodiments,
the weight ratio of iron to copper is about 100:5. In yet other specific
embodiments, the weight ratio of iron to copper is about 100:3.

[0137] Broadly, in embodiments, wherein the structural promoter is silica
sol, the iron to SiO2 weight ratio may be in the range of from about
100:1 to about 100:8; alternatively, in the range of from 100:1 to 100:7.
In embodiments, wherein the structural promoter is silica, the iron to
SiO2 weight ratio may be in the range of from about 100:2 to about
100:6. In embodiments, the weight ratio of iron to silica is in the range
of from about 100:3 to about 100:5. In embodiments, wherein the
structural promoter is silica, the iron to SiO2 weight ratio is
about 100:5. In embodiments, wherein the structural promoter is silica,
the iron to SiO2 weight ratio may be in the range of from about
100:3 to about 100:7; alternatively, in the range of from about 100: 4 to
about 100:6. In embodiments, the catalyst comprises an Fe:Cu:K:SiO2
mass ratio of about 100:4:3:5.

[0138] In embodiments, the FT catalyst is a cobalt-based catalyst. In
embodiments, the catalyst comprises cobalt, and optionally a co-catalyst
and/or promoter, supported on a support wherein the cobalt loading is at
least or about 5, 10, 15, 20, 25, 28, 30, 32, 35, or 40 percent by
weight. In embodiments, the cobalt loading is in the range of from about
5 to about 50% by weight, from about 10 to about 50% by weight, from
about 15 to about 50% by weight, from about 20 to about 50% by weight,
from about 25 to about 50% by weight, from about 28 to about 50% by
weight, from about 30 to about 50% by weight, or from about 32 to about
50% by weight. The metal dispersion for the catalytically active metal
(e.g., Co, and optionally co-catalyst and/or promoter) of the catalyst
may be in the range of from about 1 to about 30%, from about 2 to about
20%, or from about 3 to about 20%. In embodiments, the co-catalyst is
selected from the group consisting of Fe, Ni, Ru, Re, Os, oxides thereof,
and mixtures of two or more thereof. In embodiments, the catalyst
comprises at least one promoter selected from the group consisting of
Group IA, IIA, IIIB or IVB metals, oxides thereof, lanthanide metals and
oxides thereof, and actinide metals and oxides thereof. In embodiments,
the promoter is selected from the group consisting of Li, B, Na, K, Rb,
Cs, Mg, Ca, Sr, Ba, Sc, Y, La, Ac, Ti, Zr, La, Ac, Ce, Th, oxides
thereof, and mixtures of two or more thereof. The co-catalyst may be
employed at a concentration in the range of from about 0 to about 10% by
weight based on the total weight of the catalyst (i.e., the weight of
catalyst, co-catalyst, promoter and support) or from about 0.1 to about
5% by weight. The promoter may be employed at a concentration of up to
about 10% by weight based on the total weight of the catalyst, and in one
embodiment about 0.1 to about 5% by weight.

[0139] In embodiments, the catalyst comprises cobalt supported by alumina;
the loading of cobalt being at least about 25% by weight, at least about
28% by weight, at least about 30% by weight, or at least about 32% by
weight; and the cobalt dispersion is at least about 3%, at least about
5%, or at least about 7%.

[0140] In embodiments, the catalyst used in the disclosed method is a FT
catalyst as described in and/or formed via the multiple impregnation step
method described in U.S. Pat. No. 7,084,180, the disclosure of which is
hereby incorporated herein in its entirety for all purposes not contrary
to this disclosure. The catalyst can comprises at least one catalytic
metal (i.e., Co, Fe) at a loading level of about 20% by weight or more,
about 25% by weight or more, about 28% by weight or more, about 30% by
weight or more, about 32% by weight or more, about 35% by weight or more,
about 37% by weight or more, or about 40% by weight or more.

[0141] In embodiments, the FT catalyst utilized is an iron-based catalyst
and subjecting the synthesis gas to reaction conditions whereby liquid
hydrocarbons are produced comprises contacting the synthesis gas with
catalyst at a temperature in the range of from about 200° C.
(392° F.) to about 300° C. (572° F.), from about
220° C. (428° F.) to about 275° C. (527° F.)
or from about 240° C. (464° F.) to about 260° C.
(500° F.). In embodiments, the temperature of the FT synthesis is
a temperature of greater than or equal to about 200° C.
(392° F.), 220° C. (428° F.) or 250° C.
(482° F.). In embodiments, the FT synthesis is carried out at a
pressure in the range of from about 100 psig (689.5 kPa) to about 1000
psig (6894.8 kPa), from about 200 psig (1379 kPa) to about 500 psig
(3447.4 kPa) or from about 300 psig (2068.4 kPa) to about 400 psig
(2757.9 kPa). In embodiments, the FT synthesis is carried out at a
pressure of greater than or equal to about 100 psig (689.5 kPa), about
300 psig (2068.4 kPa), or about 350 psig (2413.2 kPa). In embodiments,
the FT synthesis is carried by introducing the synthesis gas into an FT
production apparatus 700, as described hereinabove. The FT production
apparatus comprises an FT synthesis reactor. In embodiments, the FT
synthesis reactor is a slurry bubble column reactor. In embodiments, the
residence time in the FT synthesis reactor is in the range of from about
1 s to about 3000 s, from about 10 s to about 500 s or from about 100 s
to about 300 s. In embodiments, the FT synthesis is carried out for a
residence time of about 100 s, about 200 s, or about 300 s.

[0142] Converting synthesis gas into product can further comprise
separating tailgas and/or spent catalyst/product from the conversion
product at 1020. In embodiments, converting synthesis gas into product
further comprises separating tailgas from the primary product(s). For
example, a tailgas comprising methane, hydrogen, carbon monoxide and/or
carbon dioxide may be separated from the synthesis gas conversion product
(e.g. liquid hydrocarbons). In embodiments, converting synthesis gas into
product further comprises separating spent catalyst/wax from the liquid
hydrocarbons. During FT synthesis of liquid hydrocarbons, spent catalyst
and associated wax is routinely removed from the slurry process. Such
catalyst can be separated from the primary liquid product via any
suitable methods known in the art, for example via centrifugation,
filtration, magnetic separation, or a combination thereof. Such separated
spent catalyst and any product that is separated therewith is referred to
herein as spent catalyst/product and may be recycled, as discussed
further hereinbelow, in step 1100.

[0143] Recycling at least one Component 1100. In embodiments, the
disclosed method of producing synthesis gas conversion product according
to this disclosure comprises recycling at least one component from
converting at 1000 for reuse in producing additional synthesis gas 800.

[0144] In embodiments, recycling at least one component 1100 comprises
recycling at least a portion of the tailgas produced while converting the
synthesis gas to product at 1000. The tailgas produced during conversion
of synthesis gas to product can be recycled for use as fuel in the
reforming step. In this manner, the `waste` tailgas can be utilized to
benefit within the system. As discussed hereinabove, one or more tailgas
recycle lines 770 may fluidly connect the FT synthesis apparatus 700 with
one or more burners 404 of reformer 400. As discussed hereinabove, carbon
dioxide may be removed from the tailgas prior to recycle for use as
fluid. This may be particularly desirable as it enables sequestration of
additional carbon dioxide within the biorefinery. All or a portion of the
tailgas exiting synthesis gas conversion apparatus 700 via tailgas outlet
line 760 can be introduced into a carbon dioxide removal apparatus,
described hereinabove, and/or recycled to reformer 400.

[0145] In embodiments, recycling at least one component 1100 comprises
recycling at least a portion of the separated spent catalyst/product and
subjecting it to reforming conditions along with carbonaceous feed
material to produce additional synthesis gas from the product (e.g.
liquid hydrocarbons) therein. For example, one or more catalyst/product
recycle lines 755 may be used to introduce spent catalyst/product into
the reformer, for example via carbonaceous feed line 250 and/or mixing
apparatus 300. In this manner, additional value can be obtained from the
reformable material separated with the spent catalyst, thus improving the
overall liquid yields of the biorefinery. Additionally, in this manner,
disposal of material is reduced and the spent catalyst (substantially
free of associated product) can be separated (e.g. with the ash) for
disposal. At least a portion of the spent catalyst/product separated from
the primary conversion product(s) at 1020 can thus be recycled through
the coiled tubes of the reformer for production of additional synthesis
gas therefrom.

[0146] While the preferred embodiments of the invention have been shown
and described, modifications thereof can be made by one skilled in the
art without departing from the spirit and teachings of the invention. The
embodiments described and the examples provided herein are exemplary
only, and are not intended to be limiting. Many variations and
modifications of the invention disclosed herein are possible and are
within the scope of the invention. Accordingly, the scope of protection
is not limited by the description set out above, but is only limited by
the claims which follow, that scope including all equivalents of the
subject matter of the claims.

[0147] The discussion of a reference is not an admission that it is prior
art to the present invention, especially any reference that may have a
publication date after the priority date of this application. The
disclosures of all patents, patent applications, and publications cited
herein are hereby incorporated herein by reference in their entirety, to
the extent that they provide exemplary, procedural, or other details
supplementary to those set forth herein.